If you want to email a contact in your .Mac Webmail Address Book, there are two ways to go about this:
Note: Don't use method 2 (click on the Address Book email address) if you're already composing a new message. If you're already composing a new message and you click an email address in your address book, you'll see an alert message that says "This message has not been sent. To close this message without sending it, click OK."