Rough time of year to be carless in Maine. How long will you be here?
The South Portland Bus Service does make a few stops in Portland proper and can get you to Rigby Yard in South Portland if you want to take a look. There aren't a lot of public/non-trespassing spots for viewing it, but the US Route 1 bridge next to PT Tower is a good spot and probably your best bet.
Maine Narrow Gauge was running steam this weekend. Not sure if they're doing anything during the week.
Mercy Hospital has two campuses: their original building on State Street, and their new satellite location on Fore River Parkway. It's the Fore River Parkway location that offers nice views of Downeasters coming on and off the Mountain Branch.
Not far from there is Mountain Junction (where the mainline and the Mountain Branch meet). There are some business parking lots off Saint John Street that offer views of the junction area.
Also nearby, offering decent train viewing, is the Veteran's Memorial Bridge, which is one of three bridges linking Portland and South Portland. Pan Am's Fore River bridge runs alongside it. There are benches and "bump-out" viewing areas on the Veteran's Bridge.
MEC407
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Pan Am Railways — Boston & Maine/Maine Central — Delaware & Hudson
Central Maine & Quebec/Montreal, Maine & Atlantic/Bangor & Aroostook
Providence & Worcester — New England — GE Locomotives