Dont think you can bar a specific address from mailing you but its quite simple to tick the offending email and then click it as a junk address, all future mail from that address goes direct to your junk box.
You can easily block email addresses or emails from a whole domain on Hotmail. Just go to "Options" (top right), look for the "Safe and Blocked sender lists".
Copy the email address or just the part from the @ onwards (for example: @hotmail.com) to block any emails from that domain, particularly useful with the spam that's going round at the moment where you get multiple emails from one domain like 69AEJEOV62340JBQ211@statementdunk.com and s**t like that.
I use it all the time to block them scammy fake bank emails and general spam. I only get 1-2 spam messages a week now.