For your old Kindle, calibre will automatically detect the Kindle and the books on it. There will be a "device" in the main icon bar, IIRC.
I'm pretty sure there's an easy way to import from a connected device without having to find the books in the device's file system manually.
(Initially I thought you were only asking about how to go from calibre to your new Kindle. I didn't realise you wanted to import books from your old Kindle into calibre)
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