- The maximizer over $\Sigma$'s
with nonnegative entries is $\Sigma=I_n$.
This follows from Slepian's lemma and the formula
$$EZ=\int_0^\infty dz\,P(Z>z)-\int_{-\infty}^0 dz\,P(Z<z), \tag{1}\label{1}$$
which holds if $Z$ is a random variable with $E|Z|<\infty$.
Indeed, by Slepian's lemma, if $(X_1,\dots,X_n)$ and $(Y_1,\dots,Y_n)$ are zero-mean Gaussian random vectors with $EX_i^2=EY_i^2$ for all $i$ and $EX_i X_j\le EY_i Y_j$ for all distinct $i,j$, then $P(\max_i X_i>z)\ge P(\max_i Y_i>z)$ for all real $z$ and, equivalently, $P(\max_i X_i<z)\le P(\max_i Y_i<z)$ for all real $z$. So, the claimed result follows immediately from \eqref{1}.
- If the $X_i$'s are exchangeable, then, similarly, the maximizer is the $\Sigma$ with all off-diagonal entries equal $-\frac1{n-1}$ (for $n\ge2$).
Indeed, in this case $\Sigma=\frac1{1-c}(I_n-c1_n1_n^\top)$ for some real $c\ne1$, where $1_n:=[1,\dots,1]^\top$, and the eigenvalues of $\Sigma$ are $\frac1{1-c}$ (of multiplicity $n-1$) and $\frac{1-cn}{1-c}$. So, $\Sigma$ is positive semidefinite iff $c\le\frac1n$ iff the off-diagonal entries $-\frac c{1-c}$ of $\Sigma$ are $\ge-\frac1{n-1}$. So, the claim for exchangeable $X_i$'s follows by \eqref{1} and Slepian's lemma.
Comment: It follows from the answer by Guillaume Aubrun that, remarkably, the exchangeability condition can be dropped -- in view of a recent proof of the longstanding simplex mean width conjecture (of which I had not known).