Calibre stores setting on a per-user basis so it sounds as if you have different settings for the normal user and Adininstrator user. The steps mentioned above will remove the settings for the current user.
The other possibility (also mentioned eariler) is that the folder holding the Calibre library was created under the Administrator user and only the Administrator user has full access to that folder (C:\CALIBRE_LIBRARY I think you said) and its contents. In that case it is necessary to log on as the Administrator user and then make sure the permissions on the C:\CALIBRE_LIBRARY folder are set to allow 'Everyone' full access to that folder and its contained files and sub-folders.
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