I\'m working on a site which I havent coded from scratch and in firebug the css files are being displayed as: style.css.pagespeed.ce.5d2Z68nynm.css with the pagespeed extens
To make mod_pagespeed reflect changes to assets immediately, you can configure LoadFromFile: https://developers.google.com/speed/pagespeed/module/domains#ModPagespeedLoadFromFile
This will not work for css/js/images served from virtual handlers, but any changes to static content will be re-optimized immediately. In addition to that, optimization itself will usually be finished a lot faster because loading assets from disk is cheaper then fetching them from http(s).
According to http://code.google.com/speed/page-speed/docs/using_mod.html#htaccess
you can turn off the module with the line ModPagespeed off
in a .htaccess file.
The best solution would be to have a non-live development environment that didn't have mod_pagespeed on at all, or where it could be added only for some final testing.
If you're using a W3C Total Cache plugin on WordPress you can try that to deactivate and view the file via inspect mode and always clear cache for the changes.