Open Start > Programs > Microsoft Exchange > System Manager.
Expand Administrative Groups > First Administrative Group > Servers > SMTP Backend name here > Protocols > SMTP.
Right click "Properties" on "Default SMTP Virtual Server". In "General" tab in "IP address" section press "Advanced" button. In "Advanced" window press "Add" button. Leave "(All Unassigned)" in "IP address" field and enter alternative port (for example 2525) to "TCP port" field. Press "OK" three times.