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Just my 2 cents. I think what could work is the following.
From an empty Sigil project add two blank XHTML files and in bookview add some simply formatted text to each, maybe some headers and a few paragraphs. Save this and then view with ADE, calibre and your reader.
Now reopen in Sigil and add a basic CSS file and add formatting for paragraphs and whatever headings have been used. Use Sigil to add this CSS file to both of the XHTML files, save and again view the ePub.
At this point you have shown the break between the book's content (the XHTML files) and the presentation of it (the CSS files).
Now you could show how to use classes, both in the CSS and XHTML files, to allow paragraphs to have different styling.
At this point the very basics of using Sigil and CSS have been covered, and you can now point people to fuller CSS documentation.
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