http://www.w3schools.com/css/default.asp - a basic on-line (free) tutorial. It will get you started pretty quickly.
Now, that said, you should still get a good reference book. And by that, I mean the CSS Reference published by O'Reilly. It points out a lot of the failings of IE (up through 6) and you can find work-arounds with simple Internet searches. IE 6 is more compliant than previous versions, but it still has some boogers. A lot of the boogers are still present in IE 7.
My dad uses Dreamweaver and gets pretty good results from it. Be careful with mucking with any CSS that it produces or you might not be able to get Dreamweaver to read it correctly. I hand code everything in Notepad. Old habit going back to HTML 1.0.
The real point of using CSS is to take the presentation details out of the HTML and let the HTML just be content. That was the original intent, but HTML quickly became polluted with markup tags like "<font>". With CSS, rather than using a "<font>" tag, you give an element a class (if it is a common attribute) or id (if it is specific to one instance) and then specify the formatting in the CSS file. This allows you to change the appearance of every page that uses the common CSS file by just editing that one file. If the markup is all embedded in the HTML files, you would have to change every single one to do something simple like switch all H2 headers from blue to red.
Anyway, give the tutorial a read and take a look at the CSS file Dreamweaver produces to get a feel for how it is doing things. Enjoy!