Thank you all! These are the various solutions I've looked at now from your recommendations (collected here for people with the same problem):
Dust-Me Selectors (Firefox Add-on)
This does exactly what I need. Lists used and unused CSS selectors (for the current page, or the entire site, after spidering), and can dump both lists as CSV text. Great.
https://addons.mozilla.org/firefox/addon/5392/
CSS Usage (Firefox Add-on)
https://addons.mozilla.org/firefox/addon/10704/
WARI - Web Application Resource Inspector (Java tool)
Appears to only handle static code, not dynamically generated HTML as is present in most web applications that use ajax – which, unfortunately, makes it useless, at least for me
http://wari.konem.net/
CSS Redundancy Checker (Ruby script, requires Rubygems and Hpricot)
http://code.google.com/p/css-redundancy-checker/
TopStyle (Windows-only application, $79.95 (!!))
http://svanas.dynip.com/topstyle/
These are all cross-platform and free, except for TopStyle.