For my Computer Architecture course I had to work with both a PIC and an AVR; in my opinion the PIC was easier to work with, but that's maybe because that's what we worked with the most and we had the most time to get used to. We used the AVR maybe only a couple of times so I couldn't get the hang of it perfectly but it also was nothing overly complicated, or at least not more frustrating than the other.
I think you can also order microprocessor samples from Microchip's website so you could also get started with that?
