Let me give a reasonable model for the question in the title. In ${\rm Sym}_n({\mathbb R})$, the positive definite matrices form a convex cone $S_n^+$. The probability I have in mind is the ratio $p_n=\theta_n/\omega_n$, where $\theta_n$ is the solid angle of $\Lambda_n$, and $\omega_n$ is the solid angle of the whole space ${\rm Sym}_n$ (the area of the unit sphere of dimension $N-1$ where $N=\frac{n(n+1)}2$). These definitions are relative to the Euclidian norm $\|M\|=\sqrt{{\rm Tr}(M^2)}$ ; this is the most natural among Euclidian norms, because it is invariant under unitary conjugation.
Because $S_2^+$ is a circular cone, I could compute $p_2=\frac{2-\sqrt2}4\sim0.146$ . Is there a known close formula for $p_n$? If not, is there a known asymptotics?
More generally, we may define open convex cones $$\Lambda_n^0\subset\Lambda_n^1\subset\cdots\subset\Lambda_n^{n-1}$$ in the following way: $M\mapsto\det M$ is a homogeneous polynomial, hyperbolic in the direction of the identity matrix $I_n$. Thus its successive derivatives in this direction are hyperbolic too. The $k$th derivative defines a "future cone" $\Lambda_n^k$, these cones being nested. For instance, $\Lambda_n^0=S_n^+$. It turns out that this derivative is, up to a constant, $\sigma_{n-k}(\vec\lambda)$, where $\sigma_j$ is the $j$th elementary symmetric polynomial and $\vec\lambda$ the spectrum of $M$. Therefore $\Lambda_n^k$ is defined by the inequalities $$\sigma_1(\vec\lambda)\ge0,\ldots,\sigma_{n-k}(\vec\lambda)\ge0.$$ For instance, $\Lambda_n^{n-1}$ is the half-space defined by ${\rm Tr}M\ge0$.
Let us define again $p_{n,k}$ the probability for $M\in{\rm Sym}_n$ to belong to $\Lambda_n^k$. Thus $p_{n,0}=p_n$ and $p_{n,n-1}=\frac12$.
What is the distribution of $(p_{n,0},\ldots,p_{n,n-1})$, asymptotically as $n\rightarrow+\infty$?
Edit. As Mikaël mentionned, it is equivalent, and easier for calculations, to consider the standard Gaussian measure (GOE) over ${\bf Sym}_n$.