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I think that Simultaneous Device Usage refers to the number of devices registered to a single account that has purchased the books. For example, you want to have the book on your Kindle, your spouse's Kindle, your iPhone, your Kindle for PC, etc all at the same time. The Loan Me feature is for loaning a book registered to one user's account to someone with a different Amazon account. If you go to the Manage Your Kindle account page and click the arrow next to the book title in your orders list, then you will see a button that says "Loan this book" if it is lendable.
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