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Then your content is being stored in a different folder. The options from within the Kindle app will show you where your content is being stored (and allow you to change it). Keep in mind that the file names for Kindle for PC books don't usually have the title of the book in them. They're usually the asin number with "_EBOK.azw". It's just not possible that a book you're able to read with the Kindle app doesn't physically reside on your computer.
Are you sure you haven't confused the Kindle app for the Kindle Cloud Reader (browser-based)? You won't be able to add a Cloud Reader book to calibre... even if you "download" it for offline reading. It's not a normal ebook file you can access.
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