The supplementary subset of a polyhedral subset is polyhedral. Alas, the content of a subset does not determine the content of its supplement. This makes generalizations of Gauss-Bonnet more complex.
A subset of Sn is convex if it is the intersection of some non-empty set of hemispheres. The shorter geodesic path between two points in a convex set lies within that set.
This notion bears on curvatures at vertices of polyhedra. Here.