Use Dropbox. Put the Calibre library folder in the Dropbox folder and once you install Calibre on your new PC you can simply sync with Dropbox and your new Calibre installation will look like your old one.
Be sure when you install Calibre and go through the setup you indicate the right location for the library folder.
I've used Dropbox and Calibre with three PCs and several Android devices and my Kindle to retrieve books from my library and in the case of the PCs to install my entire library on different PCs.
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