I absolutely second the Zeldman book for learning CSS. I was learning CSS, but never really understood what the big deal was, until several "eureka" moments while working through "Designing with Web Standards."
For HTML, IMHO, the best way is to start cutting code. You may want to download
TextWrangler2.0 from Bare Bones Software (it's now free). Also, consider picking up the OReilly HTML in a Nutshell, or HTML reference so you have something to refer to while learning.
Finally, make sure to begin checking out the HTML source for any web pages you visit. I'd recommend focusing on pages that do not have huge, graphic backgrounds, because these often stray from basic HTML practices. Also, the intricate graphic sites often were created using WYSIWYG apps. You should concentrate on learning basic HTML, then when (if) you finally use something like Dreamweaver or GoLive, you'll understand how these apps are helpful, and where they really suck.
Best,
Logicat