I've managed to confuse myself on a topic I thought I understood.
To set up, if a surface $M$ is a compact Riemannian manifold with boundary $\partial M$, then the Gauss-Bonnet theorem states $$\int_{M}KdS+\int_{\partial M}kds=2\pi \chi(M)$$ where $K$ is the Gaussian curvature of $M$, $k$ is the geodesic curvature of $\partial M$, and $\chi(M)$ is the Euler characteristic of the surface. Now, if our surface was $\textit{almost}$ smooth everywhere, except at some finite set of points $\left\{ x_{k}\right\}_{k\le n}\subset M$ where there were vertex singularities with angular defects $\left\{ \theta_{k}\right\}_{k\le n}$ at these points, then the Gauss-Bonnet theorem generalizes to $$\int_{M}KdS+\int_{\partial M}kds+\sum_{k\le n}\theta_{k}=2\pi \chi(M).$$ This is intuitively very pleasing, because it's essentially the statement that a surface's curvature, when viewed as a measure, can either live on the subset of the surface that's Riemannian, the boundary, or at vertices. This generalizes both Gauss-Bonnet for smooth surfaces and Descarte's theorem for the total angular defect of polyhedra.
In particular, if $M$ is a polyhedron with $n$ vertices, then $K=k=0$, and the theorem reduces to Descarte's theorem $$\boxed{\sum_{k\le n}\theta_{k}=2\pi \chi(M)}$$ This formula works beautifully for convex or toroidal polyhedra. But for some nonconvex polyhedra, I have no idea what's going on and am completely lost. To illustrate, I'll focus my attention particularly on two examples.
First, the $\textit{pentakis dodecahedron}$ is simply a regular dodecahedral surface with (short) pentagonal pyramids attached to each face. From reading its Wiki page, its Euler characteristic is $2$. No surprises here, since it has no holes or handles.
Then we come to the $\textit{small stellated dodecahedron}$, which is very similar, but with pentagonal pyramids substantially taller. It's Wiki page, Wolfram page, and this source all state, quite strangely, that it has twelve pentagrams as faces with thirty edges and only twelve vertices (which I would never even consider being the case). Its Euler characteristic then drops to $-6$. The same peculiar counting method seems to be implemented for several other nonconvex polyhedra.
I tested this by counting the small stellated dodecahedron's total angular defect, as shown here. Since each triangular face is isosceles with one angle of $36^{\circ}$ at the top and two angles of $72^{\circ}$ at the base, this is straightforward. There are twelve vertices (the pyramidal vertices) with a positive defect of $$360^{\circ}-5\cdot36^{\circ}=180^{\circ}$$ and twenty vertices (the original dodecahedron's vertices) with a defect of $$360^{\circ}-6\cdot72^{\circ}={-72^{\circ}}.$$ The total angular defect then comes to $$12\cdot 180^{\circ}-20\cdot72^{\circ}=720^{\circ}.$$ This is exactly what we would expect given that the small stellated dodecahedron has no holes or handles. This would also suggest that it has the same topology as a sphere and has an Euler characteristic of $2$. Moreover, whenever I count the vertices, edges, and faces, I get $V-E+F=32-90+60=2,$ which I'd expect anyways.
My question is, how could this $\textit{not}$ be the correct answer? My background is in analysis and differential geometry, not topology. If I'm wrong, I have no idea how. I also doubt all these sources are simultaneously wrong. But nowhere in the Gauss-Bonnet/Descarte theorem is convexity assumed. Moreover, it sounds preposterous from an analysis perspective that increasing the heights of the pentagonal pyramids to a certain point suddenly causes the total curvature to discontinuously become negative.
The sources for the stellated dodecahedron all state that this polyhedron confused early topologists. If this is just a funny way of counting faces, edges, and vertices, then who decided this was the $\text{"correct"}$ way to count them, and which way is $\text{"correct"}$ for the Gauss-Bonnet/Descarte theorem?
You are treating the small stellated dodecahedron as a collection of triangles glued together along their edges -- just the exposed shapes that you can see in the figure. You are also treating each intersection of line segments as a vertex. As a result, you end up with something that is topologically equivalent to a sphere.
But when someone says the small stellated dodecahedron is made of $12$ pentagrams, the pentgram they refer to is the star polygon $\left\{\frac52\right\}$. Although this figure looks something like a pentagon with a triangle glued to each edge, it has only $5$ vertices and $5$ edges: each edge connects one of the "points" of the "star" to another "point", and in between these two vertices is crosses two other edges without creating any additional vertices. The pentagram is a self-intersecting polygon.
So we have edges that don't end when they intersect another edge, and faces that don't end when they intersect another face. This is getting weird already, even before we calculate the Euler characteristic.
In short, the small stellated dodecahedron is not just a pentakis dodecahedron with the pyramids stretched outward to make certain faces coplanar. It's a completely different construction.
It you try to project the pentagram faces of the small stellated dodecahedron onto a concentric sphere, they will overlap each other. I find it hard to see a spherical topology in this object--if it's there, it is strangely twisted around itself, just as the pentagram is a pentagon twisted around itself--so it should be no surprise really that it does not have the same Euler characteristic.