I am not sure. I don't have an iCloud/Me account or a Windows / Outlook setup, so it would be too much work for me to test, sorry.
Honestly, I don't know what they are doing under the hood, but it seems very screwy. When I first started emailing somone, I was using their Gmail account. Then, I started using their work account and haven't sent anything to their Gmail account in at least a year. When I send them an invite, even when I put in their work email address, it sends the invite to their Gmail address anyway. I don't know what happened with Lion; it probably has something to do with all of the iCloud integration, but, in my opinion, it seems to have been done very carelessly with little testing.