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Reverse Engineering seems to be easier, I agree with theducks - most html/css tutorials are aimed more at webmasters. Much of what's applicable to web is not applicable to epub.
The layout of a typical book is pretty straightforward. I suggest you try to find sources that haven't been converted by Calibre - not to say that there is anything wrong with Calibre, it's just that Calibre converted HTML has a specific signature - specifically naming all the different CSS styles based on it's own normalization rules. If you find original good sources then the css styles typically have meaningful names that help you understand how the book was layed out.
xhtml is html - the difference is that xhtml must be 'perfect' in terms of opening and closing every tag. HTML spec is more relaxed. If you're editing stuff by hand you don't need to worry too much about xhtml - it's definitely good practice to close your own tags, but tools like Calibre/Sigil will constantly clean up after you when you make mistakes.
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