$\def\Inn{\operatorname{Inn}}$$\def\Aut{\operatorname{Aut}}$Let $G$ be a group with $Z(G) = 1$. Write $i_g$ for the inner automorphism $i_g(x) = gxg^{-1}$, and observe that $\phi i_g \phi^{-1} = i_{\phi(g)}$ for any $g \in G$ and $\phi \in\Aut(G)$. Therefore if $\phi$ commutes with each $i_g \in \Inn(G)$, i.e., $\phi \in C_{\Aut(G)}(\Inn(G))$, it follows that $i_g = i_{\phi(g)}$ for all $g \in G$, whence $\phi(g) = g$ since $Z(G)$ is trivial. Therefore the centralizer $C_{\Aut(G)}(\Inn(G))$ is trivial.
Now assume $G$ is simple. We claim that $\Inn(G) \cong G$ is characteristic in $\Aut(G)$. Let $\psi \in \Aut(\Aut(G))$, let $I = \Inn(G)$, and let $J = \psi(\Inn(G))$. Then $I \cong J \cong G$ and $I, J \trianglelefteq \Aut(G)$, so $I \cap J$ is either $I$ or trivial (as explained by OP). In the latter case we have $[I,J] \le I \cap J = 1$, so $J \le C_{\Aut(G)}(I) = 1$, a contradiction.
Bonus: It follows that we have a natural map $\Aut(\Aut(G)) \to \Aut(\Inn(G)) \cong \Aut(G)$ defined by restriction. The first paragraph above shows that (a) this map is injective, since its kernel is $C_{\Inn(G)}(\Aut(G)) = 1$, and (b) this map is surjective, since the inner automorphism $i_\phi \in \Inn(\Aut(G))$ maps to $\phi \in \Aut(G)$. Therefore $\Aut(\Aut(G)) = \Inn(\Aut(G)) \cong \Aut(G)$.
This is all essentially abstract nonsense and it is not necessary to use any deep facts about finite simple groups such as Schreier's hypothesis. In fact we do not need to assume $G$ is finite.