Applying Mecanim differently?

So I've watched a few tutorials on Mecanim, but none of them touched on something that I need to know. The blend tree editor is an absolutely wonderful system that allows me to visually do what previously I had a very ugly (albeit highly similar) system for. I also love that it's able to animate my characters regardless of what its bones' names are.

However, what I want to do is to shift my character's animation states directly via scripting, and shift characters into entirely new states on the fly. IE: My character has a "walk" state but no "fly" state, but I want to shift him into an arbitrary "fly" state I've set up for another character.

Is this sort of thing possible, and if so where's a reliable source to read up on Mecanim scripting?