There currently is a community uncapper that lets you specify how high skills can go, how fast skills advance relative to the vanilla speed, how much each skill contributes to levelling, etc. Check out the Nexus for it. ^^
Edit: Hmmm... now that I think about it, is it possible in the CK to set skills in NPCs higher than 100, or to get the game to generate monsters and NPCs with skill levels over 100?