EDIT I can now include the other cases, not just when the roots are distinct.
Under the transformation $(o,i) \mapsto (o + b i , i)$, we have
$\hat{\Psi}_0 (b) = \Psi_0 + 4 b \Psi_1 + 6 b^2 \Psi_2 + 4 b^3 \psi_3 + b^4 \Psi_4
\\
\hat{\Psi}_1 (b) = \Psi_1 + 3 b \Psi_2 + 3 b^2 \Psi_3 + b^3 \psi_4
\\
\hat{\Psi}_2 (b) = \Psi_2 + 2 b \Psi_3 + \Psi_4
\\
\hat{\Psi}_3 (b) = \Psi_3 + b \Psi_4
\\
\hat{\Psi}_4 (b) = \Psi_4 .
$
We are interested in the roots of $\hat{\Psi}_4 (b) = 0$ which is quartic in $b$ and so can be written,
$
\hat{\Psi}_0 (b) = \Psi_4 (b-b_1) (b-b_2) (b-b_3) (b-b_4) .
$
Below we will often use this together with the obvious formula:
$
\hat{\Psi}_1 (b) = {1 \over 4} {d \over d b} \hat{\Psi}_0 (b)
\\
\hat{\Psi}_2 (b) = {1 \over 3} {d \over d b} \hat{\Psi}_1 (b)
\\
\hat{\Psi}_3 (b) = {1 \over 2} {d \over d b} \hat{\Psi}_2 (b)
\\
\hat{\Psi}_4 (b) = {d \over d b} \hat{\Psi}_3 (b) = \Psi_4 .
$
CASE (1) First we consider the case where the four roots $b_1, b_2, b_3, b_4$ are distinct. Write
$\rho_1^A := o^A + b_1 i^A \\
\rho_2^A := o^A + b_2 i^A \\
\rho_3^A := a^A + b_3 i^A \\
\rho_4^A := a^A + b_4 i^A$
Then $\hat{\Psi}_0 = 0$ implies the 4 equations for $\alpha , \beta , \gamma, \delta$:
$\alpha_{(A} \beta_B \gamma_C \delta_{D)} \; \rho_1^A \rho_1^B \rho_1^C \rho_1^D = 0
\\
\alpha_{(A} \beta_B \gamma_C \delta_{D)} \; \rho_2^A \rho_2^B \rho_2^C \rho_2^D = 0
\\
\alpha_{(A} \beta_B \gamma_C \delta_{D)} \; \rho_3^A \rho_3^B \rho_3^C \rho_3^D = 0 \\
\alpha_{(A} \beta_B \gamma_C \delta_{D)} \; \rho_4^A \rho_4^B \rho_4^C \rho_4^D = 0$
which reduce to the 4 equations:
$(\alpha_A \rho_1^A) (\beta_B \rho_1^B) (\gamma_C \rho_1^C) (\delta_D \rho_1^D) = 0 \quad Eq 1
\\
(\alpha_A \rho_2^A) (\beta_B \rho_2^B) (\gamma_C \rho_2^C) (\delta_D \rho_2^D) = 0 \quad Eq 2
\\
\\
(\alpha_A \rho_3^A) (\beta_B \rho_3^B) (\gamma_C \rho_3^C) (\delta_D \rho_3^D) = 0 \quad Eq 3
\\
(\alpha_A \rho_4^A) (\beta_B \rho_4^B) (\gamma_C \rho_4^C) (\delta_D \rho_4^D) = 0 \quad Eq 4
$
Now we use that for spinors, $\alpha_A \rho^A = 0$ if and only if $\alpha$ is proportional to $\rho$ (we write $\alpha_A = \lambda \rho_A$).
We are considering the case where all the roots $b_1,b_2,b_3,b_4$ are all different and as such that the spinors $\rho_1 , \rho_2 , \rho_3 , \rho_4$ are not proportional to each other. Then Eq 1 is zero if and only if one of at least one of the brackets vanish. Say the first bracket is one that vanishes, so we can say $\alpha_A = \lambda_1 \rho_{1 A} = \lambda_1 (o_A + b_1 i_A)$. The first bracket in Eq 2 cant then vanish because $\rho_1$ is not proportional to $\rho_2$, and so one of the other brackets must vanish. Say the second bracket is one that vanishes, and so $\beta_A = \lambda_2 \rho_{2A} = \lambda_2 (o_A + b_2 i_A)$. The first two brackets of Eq 3 cant vanish, so at least one of the other two vanish, say it is the 3rd bracket then $\gamma_A = \lambda_3 \rho_{3A} = \lambda_3 (o_A + b_3 i_A)$. The first 3 brackets of Eq 4 can't vanish and so it must be the last bracket that vanishes, and so $\delta_A = \lambda_4 \rho_{4A} = \lambda_4 (o_A + b_4 i_A)$. And So $\Psi_{ABCD} = \alpha_{(A} \beta_B \gamma_C \delta_{D)}$ where the spinors $\alpha_A , \beta_A , \gamma_A , \delta_A$ are all distinct and each representing a principal null direction.
CASE (2) We consider the case where just two roots coincide, say $b_1=b_2$. As $\rho_1 = \rho_2$ we have three independent equations from $\hat{\Psi}_0 = 0$:
$(\alpha_A \rho_1^A) (\beta_B \rho_1^B) (\gamma_C \rho_1^C) (\delta_D \rho_1^D) = 0 \quad Eq 5
\\
(\alpha_A \rho_3^A) (\beta_B \rho_3^B) (\gamma_C \rho_3^C) (\delta_D \rho_3^D) = 0 \quad Eq 6
\\
(\alpha_A \rho_4^A) (\beta_B \rho_4^B) (\gamma_C \rho_4^C) (\delta_D \rho_4^D) = 0 \quad Eq 7
$
Then Eq 5 is zero if and only if one of at least one of the brackets vanish. Say the first bracket is one that vanishes, so we can say $\alpha_A = \lambda_1 \rho_{1 A} = \lambda_1 (o_A + b_1 i_A)$. The first bracket in Eq 6 cant then vanish because $\rho_1$ is not proportional to $\rho_3$, and so one of the other brackets must vanish. Say the second bracket is one that vanishes, and so $\beta_A = \lambda_3 \rho_{3A} = \lambda_3 (o_A + b_3 i_A)$. The first two brackets of Eq 3 cant vanish, so at least one of the other two vanish, say it is the 3rd bracket then $\gamma_A = \lambda_4 \rho_{4A} = \lambda_4 (o_A + b_4 i_A)$.
It can easily be shown that with parameter $b = b_1 (= b_2)$ $\hat{\Psi}_0$ and $\hat{\Psi}_1$ will vanish. So we also have the equation
$\alpha_{(A} \beta_B \gamma_C \delta_{D)} \; \rho_1^A \rho_1^B \rho_1^C i^D = 0$
or
$\rho_{1(A} \rho_{3B} \rho_{4C} \delta_{D)} \; \rho_1^A \rho_1^B \rho_1^C i^D = 0$
which reduce to
$(\rho_{1A} i^A) (\rho_{3B} \rho_1^B) (\rho_{4C} \rho_1^C) (\delta_{D} \rho_1^D) = 0$
implying $\delta_A = \rho_{1A} = \lambda_1 (o_A + b_1 i_a)$. So now we have that $\Psi_{ABCD} = \alpha_{(A} \beta_B \gamma_C \delta_{D)}$ where the spinors $\alpha_A , \beta_A , \gamma_A , \delta_A$ each represent a principal null direction with two directions coinciding.
CASE (3) Three roots coincide and $b = b_1 (= b_2 = b_3)$. As $\rho_1 = \rho_2 = \rho_3$ we have two independent equations from $\hat{\Psi}_0 = 0$:
$(\alpha_A \rho_1^A) (\beta_B \rho_1^B) (\gamma_C \rho_1^C) (\delta_D \rho_1^D) = 0 \quad Eq 8
\\
(\alpha_A \rho_4^A) (\beta_B \rho_4^B) (\gamma_C \rho_4^C) (\delta_D \rho_4^D) = 0 \quad Eq 9
$
Then Eq 8 is zero if and only if one of at least one of the brackets vanish. Say the first bracket is one that vanishes, so we can say $\alpha_A = \lambda_1 \rho_{1 A} = \lambda_1 (o_A + b_1 i_A)$. The first bracket in Eq 9 cant then vanish because $\rho_1$ is not proportional to $\rho_4$, and so one of the other brackets must vanish. Say the second bracket is one that vanishes, and so $\beta_A = \lambda_4 \rho_{4A} = \lambda_4 (o_A + b_4 i_A)$.
It is easily shown that with parameter $b = b_1 (= b_2 = b_3)$ $\hat{\Psi}_0$, $\hat{\Psi}_1$ and $\hat{\Psi}_2$ will vanish simultaneously. So we also have the equations
$\alpha_{(A} \beta_B \gamma_C \delta_{D)} \; \rho_1^A \rho_1^B \rho_1^C i^D = 0 \quad Eq 10
\\
\alpha_{(A} \beta_B \gamma_C \delta_{D)} \; \rho_1^A \rho_1^B i^C i^D = 0 \quad Eq 11
$
Eq 10 is
$\rho_{1(A} \rho_{4B} \gamma_C \delta_{D)} \; \rho_1^A \rho_1^B \rho_1^C i^D = 0
$
which reduces to
$(\rho_{1A} i^A) (\rho_{4B} \rho_1^B) (\gamma_C \rho_1^C) (\delta_{D} \rho_1^D) = 0
$
This implies that $\gamma_A = \lambda_1 \rho_{1A} = \lambda_1 (o_A + b_1 i_A)$. Eq 11 then reads
$
\rho_{1(A} \rho_{4B} \rho_{1C} \delta_{D)} \; \rho_1^A \rho_1^B i^C i^D = 0
$
which reduces to
$
(\rho_{1A} i^A) (\rho_{4B} \rho_1^B) (\rho_{1C} i^C) (\delta_{D} \rho_1^D) = 0
$
which means that $\delta_{D} = \rho_{1D} = \lambda_1 (o_a + b_1 i_A)$. So now we have that $\Psi_{ABCD} = \alpha_{(A} \beta_B \gamma_C \delta_{D)}$ where the spinors $\alpha_A , \beta_A , \gamma_A , \delta_A$ each represent a principal null direction with three directions coinciding.
CASE(4) Two distinct double roots $b_1$ and $b_2$. As $\rho_1 = \rho_3$ and $\rho_2 = \rho_4$ we have two independent equations from $\hat{\Psi}_0 = 0$:
$(\alpha_A \rho_1^A) (\beta_B \rho_1^B) (\gamma_C \rho_1^C) (\delta_D \rho_1^D) = 0 \quad Eq 12
\\
(\alpha_A \rho_2^A) (\beta_B \rho_2^B) (\gamma_C \rho_2^C) (\delta_D \rho_2^D) = 0 \quad Eq 13
$
Then Eq 12 is zero if and only if one of at least one of the brackets vanish. Say the first bracket is one that vanishes, so we can say $\alpha_A = \lambda_1 \rho_{1 A} = \lambda_1 (o_A + b_1 i_A)$. The first bracket in Eq 13 cant then vanish because $\rho_1$ is not proportional to $\rho_4$, and so one of the other brackets must vanish. Say the second bracket is one that vanishes, and so $\beta_A = \lambda_2 \rho_{2A} = \lambda_2 (o_A + b_2 i_A)$.
It is easily shown that with parameter $b = b_1$ we have $\hat{\Psi}_1 = 0$
$\alpha_{(A} \beta_B \gamma_C \delta_{D)} \; \rho_1^A \rho_1^B \rho_1^C i^D = 0 $
or
$\rho_{1(A} \rho_{2B} \gamma_C \delta_{D)} \; \rho_1^A \rho_1^B \rho_1^C i^D = 0$
which reduces to
$(\rho_{1A} i^A) (\rho_{2B} \rho_1^B) (\gamma_C \rho_1^C) (\delta_D \rho_1^D) = 0$
So that at least one of the last two brackets vanish. Say the third bracket vanishes, then $\gamma_A = \lambda_1 \rho_{1A} = \lambda_1 (o_A + b_1 i_A)$.
It is easily shown that with parameter $b = b_2$ we have $\Psi_1 = 0$
$\alpha_{(A} \beta_B \gamma_C \delta_{D)} \; \rho_2^A \rho_2^B \rho_2^C i^D = 0 $
or
$\rho_{1(A} \rho_{2B} \rho_{1C} \delta_{D)} \; \rho_2^A \rho_2^B \rho_2^C i^D = 0$
which reduces to
$(\rho_{1A} \rho_2^A) (\rho_{2B} i^B) (\rho_{1C} \rho_2^C) (\delta_D \rho_2^D) = 0$
So that at least one of the last two brackets vanish. Say the third bracket vanishes, then $\delta_A = \lambda_2 \rho_{2A} = \lambda_2 (o_A + b_2 i_A)$. So now we have that $\Psi_{ABCD} = \alpha_{(A} \beta_B \gamma_C \delta_{D)}$ where the spinors $\alpha_A , \beta_A , \gamma_A , \delta_A$ each represent a principal null direction with two different pairs repeated.
CASE(5) All roots coincide and we have for $b=b_1$ that $\hat{\Psi}_0 = \hat{\Psi}_1 = \hat{\Psi}_2 = \hat{\Psi}_3 = 0$. We have the equations:
$\alpha_{(A} \beta_B \gamma_C \delta_{D)} \; \rho_1^A \rho_1^B \rho_1^C \rho_1^D = 0 \quad Eq 14
\\
\alpha_{(A} \beta_B \gamma_C \delta_{D)} \; \rho_1^A \rho_1^B \rho_1^C i^D = 0 \quad Eq 15
\\
\alpha_{(A} \beta_B \gamma_C \delta_{D)} \; \rho_1^A \rho_1^B i^C i^D = 0 \quad Eq 16 \\
\alpha_{(A} \beta_B \gamma_C \delta_{D)} \; \rho_1^A i^B i^C i^D = 0 \quad Eq 17$
Eq 14 reduces to
$(\alpha_A \rho_1^A) (\beta_B \rho_1^B) (\gamma_C \rho_1^C) (\delta_D \rho_1^D) = 0$
At least one of the brackets vanish, say the first. So that $\alpha_A = \lambda_1 \rho_{1A} = \lambda_1 (o_A + b_1 i_A)$. Eq 15 reduces to
$(\rho_{1A} i^A) (\beta_B \rho_1^B) (\gamma_C \rho_1^C) (\delta_D \rho_1^D) = 0$.
At least one the last three brackets vanish, say the second bracket vanishes. Then $\beta_A = \lambda_1 \rho_{1A} = \lambda_1 (o_a + b_1 i_A)$. Eq 16 reduces to
$(\rho_{1A} i^A) (\rho_{1B} i^B) (\gamma_C \rho_1^C) (\delta_D \rho_1^D) = 0$.
At least one the last two brackets vanish, say the third bracket vanishes. Then $\gamma_A = \lambda_1 \rho_{1A} = \lambda_1 (o_a + b_1 i_A)$. Eq 17 reduces to
$(\rho_{1A} i^A) (\rho_{1B} i^B) (\rho_{1C} i^C) (\delta_D \rho_1^D) = 0$.
The last bracket must vanish, therefore $\delta_A = \lambda_1 \rho_{1A} = \lambda_1 (o_a + b_1 i_A)$. So now we have that $\Psi_{ABCD} = \alpha_{(A} \beta_B \gamma_C \delta_{D)}$ where the spinors $\alpha_A , \beta_A , \gamma_A , \delta_A$ each represent a principal null direction with all four directions coinciding.