Smashwords isn't a bad way to get your book out there, and they do offer guidance on how to format your book for the best output on their site. Although more exotic layouts might strain their system, your basic chapter and paragraph book should render just fine there.
Keep in mind, though, that a lot of people upload books to Smashwords... you could have as much of a visibility problem there as anywhere else... don't just assume you'll see "loads of hits" just by virtue of being there. (Same thing goes for the Kindle store.) The secret is in your marketing, whatever your book's location, to generate sales. (With successful marketing, your own site or a Paypal site might do as well).
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