When I installed version 1.0 of gpg4win I didn’t have any posibilities to sign/verify or encrypt/decrypt any mail. There were no sign of the whole thing on the toolbar or in the menu but the GPGol were available and checked deep down the menu of Outlook.
Earlier I had installed 0.9.3 of the gpgol plugin and back then you were supposed to manually copy a couple of files wo the windows catalog and also register a dll manually. (I’ve been trying out Thunderbird for a few months and not been using Outlook at all during that period.)
I had to manually delete those files (gpgme.dll and libgpg-error.dll that I had copied to system32), unregister the dll (gpgol.dll), start Outlook with the dll unregistered, then register the dll (gpgol.dll again) that came with the new relese before I got it working.