The fact that $A$ is positive gives us no information about $S$. In particular: if $B$ were some arbitrary matrix, then we could select a $k>0$ that is sufficiently large to ensure that $A + kI = B$ is positive definite, but the resulting skew-symmetric parts $\frac 12(A + A^T)$ and $\frac 12 (B + B^T)$ would be the same.
So with that said, the question is simply that of finding the eigenvalues of a skew symmetric matrix. I will stick to the case where $n = 2m$ is even for ease of discussion; the situation is essentially the same for the odd case, but $S$ is guaranteed to have at least one "extra" $0$ eigenvalue.
As suggested in the comments, we could use the fact that $S$ is skew-symmetric, which means that $iS$ is Hermitian. Because the eigenvalues of $S$ have the form $\pm \lambda_1 i, \pm \lambda_2 i, \dots , \pm \lambda_m i$ for $\lambda_1 \geq \cdots \geq \lambda_m \geq 0$, it follows that the matrix $iS$ is Hermitian with eigenvalues $\pm \lambda_1,\dots,\pm \lambda_m$. Thus, we could use the Rayleigh quotient to find this eigenvalues. In particular, we have
$$
\lambda_1 = \max_{x \in \Bbb C^n, \|x\| = 1} x^* (iS)x,
$$
where $x^*$ denotes the conjugate-transpose of $x$. Once we found the vector $x_1$ for which $Sx_1 = \lambda_1 i x_1$, it immediately follows that
$$
S \bar x_1 = \overline{S x_1} = \overline{\lambda_1 i x_1} = -\lambda_1 i \bar x_1,
$$
so we get two eigenvalues for the price of one. We could proceed iteratively in several ways from there. For instance, we have
$$
\lambda_2 = \max_{x \in \Bbb C^n, \|x\| = 1, x \perp x_1,\bar x_1} x^*(iS)x,
$$
and so forth. Equivalently, we can work with real numbers: we have
$$
\lambda_1 = \max_{x \in \Bbb R^{2n}, \|x\| = 1}x^T \pmatrix{0 & -S\\ S & 0} x.
$$
There are other methods as well. For instance, we could use $S^2$ instead of $iS$, noting that $S^2$ is symmetric and negative semidefinite, and its eigenvalues have the form $-\lambda_1^2,\dots,-\lambda_m^2$, each with multiplicity two. Also, instead of using the Rayleigh quotient, we could apply other algorithms such as the Jacobi algorithm or the QR algorithm.