If you want to change the appearance or styling of an element, use Firefox's Firebug extension, or similar developer tools in other browsers. Firebug will tell you exactly what style rules apply to any given element, and let you temporarily edit them and see the result immediately.
If you want to change some output text on your site, use the admin > Tools > Developers Toolkit, enter a distinctive bit of the text you want to change, select all files and search. Among the results will be the file and line number where the text is defined. You can then edit that file and save it to your template override folder.
There have been posts with listings of what various items in the stylesheet do, but I found them quite limited in usefulness and not worth the time to refer to.