When you buy a book or a subscription you choose which device it goes to. I have four accounts, a K1, my DXG, my Mom's DXG, and Kindle4PC. The items you select for a specific account will go to that device when you turn on whispernet.
If you do not want to use Whispernet, you can choose to sideload content. You go to your "Manage my Kindle" and choose to download a book to your computer. Then you drag the book from your computer to your Kindle.
While you are in your Kindle Account, you can choose to send a book to any device by selecting the book in your archive and choosing the device you want it to go to using a drop down menu.
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