I think the largest involution centralizers relative to $|G|$ arise in the alternating groups $A_n$. The index of the centralizer of $(1,2)(3,4)$ is about $n(n-1)(n-2)(n-3)/8 < n^4/8$ where $n < \log |G|$.
In groups of Lie type in odd characteristic, the largest involution centralizers are roughly groups of Lie type with rank one or two smaller. So in ${\rm SL}_n(q)$ for example, the largest involution centralizer, for odd $n$ and $q$, is isomorphic to ${\rm GL}_{n-1}(q)$. So, very roughly, the simple group has order about $q^{n^2-1}$ and the largest involution centralizer has order about $q^{(n-1)^2}$, so the index is something like $\exp (O((\log |G|)^{1/2}))$ which is larger as function of $|G|$ than in $A_n$.
The involution centralizers are a little different in even characteristic groups of Lie type, but again their index is roughly $q^n$ with $|G|$ about $q^{n^2}$.