Here's some intuition for Gauss-Bonnet. Integrating curvature over a region gives you the holonomy around its boundary.
Let me try to elaborate on that a bit. Holonomy is how much a vector gets rotated by when it is parallel-transported along a curve. On the sphere, you can see that, if you have a triangle, the sum of the angles is bigger than 180, by a factor proportional to its area--this is plausible by inspection and there's a simple geometric proof that I will skip to save time. The triangle is made out of geodesics. A geodesic, according to one definition, is a curve such its tangent vectors get parallel transported to tangent vectors of the same length. So, you can send a tangent vector to a geodesic on a little journey around the triangle by parallel transporting it. Start at a vertex, tangent to one of the sides. Parallel transport to the next vertex. Then, rotate the vector, so that it is tangent to the next side, but make it point outwards, so that you rotate by the angle at that vertex (vertical angles). Parallel transport to the next vertex and rotate again. Then repeat one more time. The vector just ends up 180 degrees from where it started. If you didn't do those rotations at each vertex, you would get the holonomy, which is the sum of the angle minus 180. So, on the sphere at least, if you understand this, then you should understand why holonomy is proportional to the integral of the curvature, which in this case (let's say unit sphere), is just the area.
Next, you can understand curvature as essentially the holonomy around an infinitesimal loop. So, kind of like Stokes theorem (actually, this follows from a version of it, involving Lie algebra-valued differential forms), if you want the holonomy around a big loop, you can just consider the region it bounds subdivide it, add up the holonomies around all the little tiny subdivided loops. So, again, you are essentially integrating the curvature to get the holonomy.
So, that's the local version of Gauss-Bonnet. Integrate curvature, get holonomy.
What's relevant here, though, is the global version of Gauss-Bonnet. This requires the notion of an Euler characteristic of a surface.
You can divide the surface up into geodesic triangles and see what happens when you add the integrals over each region together. I'm too lazy too carry the rest out, but the upshot is that the result has to be positive for a sphere, so it couldn't come from integrating a negative curvature over the sphere. It's easy to do the combinatorics for a simple example, but to prove that it doesn't depend on which example you choose requires the topological invariance of the Euler characteristic, which I would prove using homology theory.
So, a space homeomorphic to the sphere can never have negative curvature everywhere.