If you want to take part in the kindle select program, which means you will have a chance of promoting your book by free lending, you can't publish on smashwords within 90 days.
From my experience, smashwords better fits those who have not a specific e-reading device. And I guess, their readers are lesser than amazon, thus your title will have a better chance to be found. But usually, a lower price on smashword is better.
If you don't use kindle select, I don't see any reason not using smashwords. The software is great!
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