Work out some simple rules that work for you (or your company).
Divide your CSS into separate files, such as:
layout.css
content.css
menu.css
typography.css
Decide what declarations will go in each file, for example, ensure:
font-weight, text-decoration, font-family
and
h1, h2, h3, h4, h5, h6, a, p, li
All reside in the typography CSS file. Decide what to do for edge cases, such as border properties on headers, padding and margins on text elemants (layout or typography).
If your sets of declarations are getting unwieldy, some people like to organise them alphabetically.
Indent your css, for example:
#logo h1 {text-indent: -9999px}
#logo h1 a {display: block; width: 200px; height: 98px; backround...}
Comment your CSS, including references to other files if other rule for that specific selector reside there.
If you do divide you CSS into separate files, consider consolidating and compressing them into one file as part of your build & deployment process.
Make sure every developer is well aware of your standard for CSS.
Also, somewhat relevant, I've just been made aware of a Firefox plugin for finding unnecessary selectors. It's called Dust-Me Selectors.
