As a general HTML5 starting template, Boilerplate is always a good choice.
It will optimize and chain all your scripts and CSS files, as well as your HTML code and images, it also comes with useful tools like Modernizr.
If you are looking for JavaScript libraries, YUI is a very good library when it comes to UI, though maybe a little more complicated than jQuery or jQuery UI at first. I found it better than jQuery UI, and can work together with jQuery anyway.
EDIT
You may also be interested in Ext JS. Looking at the demo it provides, seems really like a powerful library with many ready to use UI widgets. Never used it though, and looks like it only offers a commercial license.