MIPS is pretty easy, though, as with nearly all RISC CPUs, there's some daft stuff about how to load 32bit constants in to registers (all instructions are 32bits long, so you can't have a 32bit operand!). But frankly RISC CPUs are easier in general to code in assembler than Intel ones because the instruction set is so much simpler and symmetric (all things can be done with all registers). And, if I remember correctly, R0 is always 0.
PSP homebrew is practically finished, just a few of the popular projects still going - media players etc. If you can get your PS2 up and running then that would be something. Or you could get a DS and learn ARM instead

ARM, MIPS, SH are all pretty similar.
Jim