After thinking a little, the best look and feel can only be achieved with extensions that let you tweak them (i.e., everyone has preferences.) So my pick goes for Stylish.
It lets you apply CSS to almost anything that can be represented in Firefox, even XUL!
An example of it, I've messed with my history menu to make it unique, here is how it looks after some work (CSS3 on the XUL omg omg):

Okay, it's not a full-blown application. but Stylish and userstyles.org are for CSS what Greasemonkey and userscripts.org are for JavaScript, so possibilities for a "rich look and feel" are almost unlimited.