What about the PS3's processor makes it that much more powerful (according to what I've heard/read/seen) and why is it actually all that difficult to program for?
It can effectively handle up to 6 processes at a time with the SPE's. Also, if coded correctly, an SPE can process more than one thing at a time, so you can double that. They're also very fast and can shred through a lot of info at once. That's where the Cell's power lies, is in the SPE's.
Naughty Dog also said that with Uncharted 2 they we're using the Cell for a lot of the graphics processing while also relying on the Cell for the animations, physics, AI, and everything else. A true feat indeed.