The situation is that you have foo.css and foo.css.gz on disk, and want Apache to serve foo.css.gz directly if asked for foo.css and the clients accepts the compressed content.
I guess that's going to be based on content negotiation with MultiViews, but a google search suggests there are practical issues to get this right that may not be obvious at first.
And also a curiosity: After all these years, why doesn't mod_deflate do this by itself? Compressing with max ratio to disk on a first request, and serving the cached .gz in subsequent requests?