Here are the important settings for communicating with the Exchange Server:
NOTE: The syntax of each setting will be shown in the Example configuration.
One potential problem that you may run into is SMTP Authentication. Basically, this means that you need to provide a username and password to use SMTP to send email. I have found no official documentation which states that Pine supports SMTP Authentication (more so on the contrary). The closest thing I've found is the possibility of a /user Parameter to the smtp-server setting, which was mentioned briefly in the change log from version 4.20 to 4.21. It was also brought up a couple of times on the listserv. (see Resources)
If you still have problems with it, here is an alternative which I ended up using. You can have your SysAdmin add your IP address to the Exchange Server to allow you to bypass the SMTP authentication.