I should concur with the other answers that there is no substitue for reading up in good texts and WP.
You are right that, in a given basis, there is a similarity (equivalence) transformation implied in the equation of your title: it basically means that the tensor product on the l.h.s. is reducible, by an orthogonal basis change to the r.h.s.; that is, in words,
- The Kronecker product of two 2-vectors (spinors; in general you have (2s+1)-dim vectors!) is a 4-vector. But rotations keep two subspaces in it separate: a 3-vector subspace, and a 1-vector (scalar) subspace. However, this is invisible to the naked eye. There is an orthogonal basis change, the Clebsch matrix, which visibly separates these two subspaces, so rotations act on these visibly separately, by block matrix action. (In your singlet case, by no action at all! the rotation matrices are the identity, 1).
Can you find this 4×4 Clebsch matrix $\cal C$ in Problem 4 here for your exact problem? (Hint: mix up just the 2nd and 3rd components by a rotation of $\pi/4$.) The "right is detail in left" convention in the tensor product amounts to
$$
\begin{pmatrix} a_1\\a_2\end{pmatrix} \otimes \begin{pmatrix} b_1\\b_2\end{pmatrix} = \begin{pmatrix} a_1 b_1\\a_1 b_2 \\ a_2 b_1\\ a_2 b_2\end{pmatrix} \leadsto \begin{pmatrix} \uparrow \uparrow\\ \uparrow \downarrow \\ \downarrow \uparrow\\ \downarrow \downarrow \end{pmatrix} ,
$$
in the spherical basis notation. The second and 3rd component, then mix up into $(\frac{\uparrow \downarrow + \downarrow\uparrow }{\sqrt{2}},\frac{\uparrow \downarrow - \downarrow\uparrow }{\sqrt{2}} )$, the triplet component and the singlet component.
The upshot is a direct sum of a 3-vector (components 1,2, & 4) and a singlet (component 3):
$$
\begin{pmatrix} \uparrow \uparrow\\ \frac{\uparrow \downarrow + \downarrow\uparrow }{\sqrt{2} } \\ \downarrow \downarrow \end{pmatrix} \oplus \frac{\uparrow \downarrow - \downarrow\uparrow }{\sqrt{2}} .
$$
Your title formula, however, never picks a basis.
Finally, there are elaborate formulas for recursive compositions of spins, pioneered by Bethe and elaborated by several authors afterwards. Your case is particularly simple, as WP details. I copy the WP formula, which uses dimensionality, instead of spin indices (2s+1 instead of your s), since you can do instant arithmetic checks by ignoring the circles in × and + !
Combining n doublets (your spin 1/2s) nets you
$$
{\mathbf 2}^{\otimes n} = \bigoplus_{k=0}^{\lfloor n/2 \rfloor}~
\Bigl( {n+1-2k \over n+1} {n+1 \choose k}\Bigr)~~({\mathbf n}+{\mathbf 1}-{\mathbf 2}{\mathbf k})~,$$
where $\lfloor n/2 \rfloor$ is the integer floor function;
the number preceding the
boldface irreducible representation dimensionality (2 s+1) label indicates multiplicity of that
representation in the representation reduction. The random walk that takes you there reconstructs the celebrated Catalan's triangle.
For instance, from this formula, addition of three spin 1/2 s yields a spin 3/2 and two spin 1/2s, ${\mathbf 2}\otimes{\mathbf 2}\otimes{\mathbf 2}={\mathbf 4}
\oplus{\mathbf 2}\oplus{\mathbf 2} $; four spin 1/2 s yields two singlets, three spin 1 s, and one spin 2, and so forth.