Bookstores have some great books published by Macromedia press, as well as others. A copy of the MX bible is a must (though not so much for Fireworks as for DW and Flash).
The Macromedia website has some tutorials, and there's craploads of stuff out on the web.
Of course, the best way to learn is to just use it constantly. Start simple and get more complex as you go.
You can also take classes for the Macromedia products as well. Either the expensive professional classes directly from Macromedia, or smaller classes from community colleges.
I took courses from Macromedia for both DW and Fireworks, but I took a community college course for Flash.
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