A few thoughts:
1) The stylesheet is linked to the html files in the <head> section
<head>
....
<link href="../../styles/default.css" rel="stylesheet" type="text/css"/>
</head>
2) Have you considered using Calibre or Sigil to edit the ebook rather than a simple text-editor? (They give you full control over the html.) The upside is that with the tools: dealing with the spine, toc.ncx, and inline TOC is much easier. And the debug tool is very handy.
3) CSS3 is a superset of CSS2. What CSS3 features are you considering (and have you checked that ereaders support it)?
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