ADI's Blackfin is another option since it's quite a straight forward architecture to program, yet can also do some fairly hefty DSP stuff should you choose to go down that route. It helps that the assembly language is quite sane too.
The Blackfin STAMP boards are an inexpensive (~$100 last I checked) way in, and they support the free GCC tools and uClinux.
Whatever architecture you choose I'd definitely recommend first downloading the toolchain\SDK and looking through the sample projects and tutorials - generally having a bit of a play about. You can often get quite acquainted with the architecture through simulation without even touching any hardware.
