Consider two electrical point charges $q_1$ and $q_2$ described by the total charge distribution $\rho = \rho_1 + \rho_2 = q_1 \delta(\vec{r} - \vec{r_1}) + q_2 \delta(\vec{r} - \vec{r_2})$. The total electrical potential could then be calculated by $$ \phi(\vec{r}) = \frac{1}{4 \pi \varepsilon_0} \int_V{\frac{\rho(\vec{r'})}{|\vec{r} - \vec{r'}|} d^3r'} = \frac{1}{4 \pi \varepsilon_0} \int_V{\frac{\rho_1(\vec{r'})}{|\vec{r} - \vec{r'}|} d^3r'} + \frac{1}{4 \pi \varepsilon_0} \int_V{\frac{\rho_2(\vec{r'})}{|\vec{r} - \vec{r'}|} d^3r'} = \phi_1 + \phi_2 $$ as solution of the Poisson's equation, which can be derived from Maxwell's equations.
Since $\vec{E} = - \nabla \phi$ and the gradient operator is linear we have $$\vec{E} = - \nabla \phi = - \nabla (\phi_1 + \phi_2) = - \nabla \phi_1 - \nabla \phi_2 = \vec{E_1} + \vec{E_2}$$ what the superposition principle is claiming. The superposition principle is sometimes called a postulate in electrostatics. But couldn't it be "derived" in that way?