@dschnit1 - Is the file your trying to add Blocked - look in file properties
Also check FAQ section -
calibre freezes/crashes occasionally? sometime problems manifest themselves in mysterious ways.
I see you're using 32bit calibre on a 64bit Windows, try installing the 64 bit version - you can have both installed and they will use the same settings and libraries
Also, Windows error 5 Access denied is sometimes a sign of the presence malicious software - run some stand alone malware scanners.
BR