We don't use the feature the way you are trying, but I imagine that it would be something like:
Try going to Admin panel -> Settings
Under " Alerts & Notices"
Make sure that "New Ticket Alert:" is enabled.
Then check the roles you want to receive email.
Personally we have "admin email" and "department manager" checked.
The default department email address is actually a mailing list that we use for support inquires. So all alerts get sent to that list so all staff are alerted to the fact that there is a new ticket. (I do not get dupe emails, and my personal email address is specified in the sites "admin email".
Hope that helps, or gives you an idea how to work around your issue. :)