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Unfortunately, Smashwords doesn't give you a lot of options... not even uploading your own prepared pre-formatted content. It takes Word, it does the converting... that's all the options you get.
Also, the Smashwords interface won't let you edit the copy... it'll only tell you (more or less) what you did wrong after you upload it. If you haven't used their Style Guide, I'd recommend doing so, and getting your copy as close to their recommendations as possible.
If Libre Office content can be saved as a Word doc, you may need to pass that copy to someone who has Word (or go to a service that will let you use their equipment, like a library, FedEx-Kinkos, etc) and check your new Word doc for proper formatting. If they don't have web access there, print out the Style Guide and take it with you.
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