The impact of a Web site, and its usability, depend crucially on the colour palette employed—the range of colours, and their relations with one another.
The one obvious rule is that colours should be used consistently and exclusively. For example, the colour for an unvisited hypertext link should not be used for anything but unvisited hypertext links.
Some of your colours should go together. One or two should be used for contrast—for particular jobs, or at particular spots on the page.
More about this later (I hope). In the meantime, I’d like to recommend a free tool that I find very useful. This is Sam Francke’s CPick. In return for downloading the program, Sam used to ask only that you’d send him a postcard from where you were. (I don’t know if he still does this.)
It’s a small program, with a tiny help page in idiosyncratic English, but it’s pretty intuitive to use, and there are helpful tool tips which pop up on everything. You can capture colours from any visual object on your screen; load and save colour files; put colours into a 6-slot stack; copy hex values to the clipboard, for use in your CSS files; and have a lot of fun moving the sliders to find compatible colours. And there’s more.
You can download it, with a lot of other stuff, from Sam’s Web site. I recommend it to any Web designer.