AVR is not the best instruction set. I would save it for the second or third set of commands. But in the end, you may find yourself there, as arduino is incredibly popular and has good support through the community (although asm is the exception, not the rule in this world).
right now you can get the msp430 board for $ 4.30, basically TI eats the cost to give these things away. msp430 is a good set of instructions to learn.
Armmite pro is not bad, arduino size, board, but uses a hand instead of avr. hand and thumb are good instruction sets.
There are emulators for almost everything, if not, creating an emulator is a very good way to find out how everything works. If nothing else, I usually do not recommend writing a disassembler.
Also, the set of commands with the C compiler is good in that you can write some code in C, play with optimization and see what type of assembler is output, and learn different things about assembler. Learn some tricks for efficiency and productivity first, later you can beat the compiler, or at least be on par. all of those mentioned have some kind of C compiler, avr and msp have ways to make gcc work, hands and thumb are supported by mainline compilers. Llvm is automatically a cross-compiler, so you do not need to compile the compiler to get started, the msp430 database for llvm is experimental, but should work or be close, hands and thumbs are ok (use -m32 in clang to avoid 64-bit integers numbers on a 64-bit node).
The stellaris chips, formerly a microworld, are now ti (texas instruments) good, only with a finger / thumb2. Mbed is actually pretty good, except for the blue LEDs (give me a migraine), you do not need to make a sandbox, connect a USB drive, mount it as a file system, copy your .bin file to a flash, press the reset button and it starts your program.
sparkfun.com is your friend, developer tools, and there is a long list of microcontroller-based boards from all players. The msp430 tip I mentioned is about $ 5, something there, army pro, a lot of arduino flavors, I recommend a panel for lily, it's about the same price as arduino pro, but already has a header soldered for use with small USB to serial stuff that you also want to purchase. stellaris is not represented in sparking, but many boards are less than $ 50.
The msp430, armmite pro, arduino, stellaris, mbed, and other boards need power that usually goes through a USB cable or is used for serial operation by some usb ftdi-based users.
If you are following an emulator’s route, qemu supports multiple sets of commands, hands / thumb. There are gameboy and nds emulators. I wrote one on github called thumbulator. the nds ideas emulator, in the initial form, comes with hand kernels for both arm9 and arm7, but I did not try to extract and use them myself. If you want to go to an old school, there are tons of 6502 and z80 emulators there, and some compilers believe or not, of course, assembler.
The last assembler that I would know is x86, a terrible set of commands, and with options and microcoding you will not exceed the compiler in all directions, yes your computer at that moment, but all x86 computers are not worth the time, other instruction sets are more important to know ( hand, thumb, thumb2, avr).