We examine the probability that at least two eigenvalues of an Hermitian matrix-valued Gaussian process, collide. In particular, we determine sharp conditions under which such probability is zero. As an application, we show that the eigenvalues of a real symmetric matrix-valued fractional Brownian motion of Hurst parameter $H$, collide when $H<1/2$ and don't collide when $H>\frac{1}{2}$, while those of a complex Hermitian fractional Brownian motion collide when $H<\frac{1}{3}$ and don't collide when $H>\frac{1}{3}$. Our approach is based on the relation between hitting probabilities for Gaussian processes with the capacity and Hausdorff dimension of measurable sets.