Once Shepard locks in the romance during their Game Night, she will not be able to romance anyone else. Samantha is one of a few LGBTQ+ romance options in the Mass Effect trilogy and is only available as a romantic interest for a female Shepard. Related: Mass Effect 3: How to Romance Steve Cortez
To romance Samantha, Shepard will need to get to know her and agree to take some time off for a game night in the Captain's Cabin. Shepard can choose to be nice to her to begin hinting at her interest. At first, Samantha will be somewhat nervous and flustered. When Shepard first meets Samantha in Mass Effect 3, the comms specialist will come visit the Captain's Cabin to offer a virtual tour of the new Normandy.
Several new characters join the Normandy crew in Mass Effect 3, and many of them, including Shepard's new Communications Specialist, Samantha Traynor, are romance options.