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I assume you have tried the obvious . a COMPLETE uninstall including wipe all registry entries.... , wipe app data. & wipe calibre library ( backup your appdata library contents first! )( use REVO uninstaller, or a careful manual search in regedit) then a brand new install.. once a new, empty install works, then restore your books & your preferences.
it is probably faster to just remove all traces & to start over, rather than play needle-in-a-haystack with the current messed up install.
AFAIK, calibre does not expect you to have or to get python, it should just install & work on any windows PC
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