Because the headers are a long string that is built and not an array and with all the possible From's there can be, it's not as easy as we would want.
But something quick and dirty on the mail_send hook could be...
PHP Code:
$newmailfromname = "The Mailman";
$headers = str_replace("From: $mailfromname <$from>", "From: $newmailfromname <$from>",$headers);
If all three email contacts you can set in vBulletin are the same, that should work. If users can send each other mail, you may need to check if $username is set and not do the replace.