CS4 is awesome.
In the output settings (flyout menu next to save) if you are going to generate html, make sure the slices are CSS, not table-based. Not really my cuppa tea but if you wanna do it like that, there ya go.
I'm not sure what else you want to know?
I can tell you how I learned web stuff from absolutely *nothing*, starting almost 2 years ago, it might help you.
First I borrowed a text book from a mate, was a bit old but covered HTML 4, this is the latest edition:
http://www.amazon.com/Perspectives-Creating-Comprehensive-Paperback-Technology/dp/0619268018/ref=sr_1_4?ie=UTF8&s=books&qid=1248307102&sr=1-4
I liked this book because it had historical perspective and started at the beginning. Talked about networks and how the internet started. It went through understanding HTML from each version's abilities. This gave me some understanding of how HTML has evolved and the thinking behind evolutions. When it finally got into CSS I understood just how content is supposed to be separated from design (something which I had massive difficulty explaining to a print designer friend helping design my site, it's the one thing I really dislike about it in it's current form, it's simply not accessible and to me it's broken).
Actually before I read that book I watched a total training video on Dreamweaver MX. But that is not something I recommend doing first. It trained in exactly wrong way IMO, but would be valuable if you already have the HTML/CSS understanding. Among other things, the trainer avoided the code side at one point referring to it as geeky. What a fucking dumbass.
I think then I got a book on Javascript ( http://www.amazon.com/JavaScript-Beginners-Second-John-Pollock/dp/0072227907/ref=sr_1_7?ie=UTF8&s=books&qid=1248308439&sr=1-7), have since learned a bit of flash although not the actionscript side, and learned php online. Read a book on Dreamweaver CS3( http://www.amazon.com/Dreamweaver-CS3-Missing-David-McFarland/dp/0596510438/ref=sr_1_1?ie=UTF8&s=books&qid=1248308522&sr=1-1) just because I wanted to make use of it properly. I'm not sure at what point I truely understood just how the web is a bunch of different (and usually competing) technologies cobbled together to achieve an end result. Mucking around with CMS's has given me more understanding of PHP/SQL, I'm starting to think the more I
do the more I'll understand it, perhaps to a level that some training does not cover.
Maybe not, I dunno but I'm mostly self-taught in my actual day-to-day profession and I tend to have a deeper understanding of lots of stuff than my peers, so I think the self-taught method works quite well for some people.
All of this has been interspersed with googling things that I want to know and trying to get something to work. Sometimes nicking code and dissecting it to see how it works and adapting it. Although I actually wrote some of my javascript from scratch, was kinda proud of that at the time...
Once I've finished my current project I want to get an advanced book on CSS, because every now and then I see tricks that I had no idea existed, CSS is pretty neat.
I hope some of this crap helps.