The centre of $\text{End}_A(S)$ is a field.. For,
the endomorphism ring of a simple module is a division ring.
Now we will show that the centre $Z=Z(\text{End}_A(S))$ is exactly the field $k$ because for all $0 \neq x \in Z(\text{End}_A(S))$, we always have $x^{-1} \in \text{End}_A(S)$. But we have to show is that the inverse $x^{-1} \in Z(\text{End}_A(S)).$ And this holds as for $x \in Z(\text{End}_A(S))$, we have \begin{align*} &gx=xg \ \forall g \in \text{End}_A(S), \\ \Rightarrow &x^{-1}gxx^{-1}=x^{-1}xgx^{-1} \\
\Rightarrow &x^{-1}g=gx^{-1}, \end{align*} which says $x^{-1} \in Z(\text{End}_A(S))$. Hence for $x \in Z(\text{End}_A(S))$ implies $x^{-1} \in Z(\text{End}_A(S))$. Further, note that centre of a ring is itself a ring and infact a commutative ring.
Thus $Z(\text{End}_A(S))$ being commutative ring as well having property that it consists of inverses of all its non-zero elements $(xx^{-1}=1)$, implies that $Z(\text{End}_A(S))$ is a field.
Edit: Now we have to check whether $Z(\text{End}_A(S)) =k$ or not. For this, see the answer by @egreg.