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There is also the folder containing Calibre settings under your User profile. This is important as it will contain the path (amongst other things) that Calibre will use to try and find your library. Deleting this folder makes calibre return to default settings.
It will have a path something like C:\Documents and Settings\Username\Application Data\calibre although it can vary slightly with different versions of Windows. You may need to ensure that you have the "Show Hidden Files" set under folder options to see this folder.
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