We hire very slowly and very carefully. And we draw from our personal network first. The best way to get hired by GitHub is to be in San Francisco, come to the Drinkups, write awesome open source code or make insanely beautiful designs, and be a genuinely interesting and hard working person.
As for other startups, I don't really know firsthand the culture of many of them, but I do know the founders of CrowdFlower and they're amazing. And they're hiring. Go check them out.