I am surprised you could change anything on the tmobile site that would help her email (unless she is only using the blackberry addy and not another). Generally, when you set it up on the BIS, it is polled every 10-15 minutes. In order to get instant (3-5 seconds) email, you need to go to her email server and forward a copy of the email to her
type of addy. Then remove her addy from the TMO webclient otherwise you get 2 copies of each message about 15 minutes apart.
If she is just using the BB addy directly, maybe going to the webclient and pushing the service books helped.
From Outlook, you can sync up the contact info (addresses/phone numbers, email addy), calendar, tasks & memos. I am not sure about express. But like prior responses said, it really is pretty easy. You don't want to type phone numbers etc, directly into the BB, it is much easier to get your outlook all set up and then just sync it up.