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@ayoshak - I'm a bit confused - when I read your first post I got the impression that the library already exists on the external USB drive and that you can use it from an installed version of calibre presumably on your system drive. And that what you want to do is - install the portable version of calibre onto your USB drive and use it to access the library you've built in that same drive.
That error message appears to be saying trying to write to a read only database - check the properties on the metadata.db file and make sure its not read only, if it is uncheck that setting. But I doubt that's the problem...
But I wonder if its a permissions or ownership issue. The library (and database) might be owned by user A but the USB device might owned by user B. If the portable version is installed at the root of the USB drive then I think it it will inherit the ownership/permissions from the drive. And the portable version of calibre sort of expects its library to be in something like X:\Calibre Portable\Calibre Library
Try installing calibre portable to the same area as you have the desktop version eg C:\Program Files\Calibre Portable. Then see if you can use the library from it, if it can then that will eliminate calibre portable itself as the cause of your problem.
BR
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