It depends. I started learning in school on the Motorola 6811, followed by the 6800, and finally, the 68000 (or 68K). As far as assembly languages go, I find the Motorola processors to be far less confusing and easier to code for. It's also good for learning the basics of assembly programming.
On the other side, you have the Intel processors. If you really want to learn assembly programming, I recommend starting with a simple processor (like the 6811 or 6800) and then working your way up. That way, you have the fundamentals in place and don't get distracted or confused by the plethora of (advanced) features in more modern processors.
There are numerous tutorials available on the web (just search on Google). Find one that works for you and that you're comfortable with.