Hey there!
So you can, but Samantha is an exclusive romance, so it's only an option if you aren't committed (The most common commitment people stumble into is dommy or subby Mason, both of whom do not share with how they come to be).
For a reason in the romance, you will need to complete Mason's storyline (Talk to him in chapter 2, go through his story, but choose not to make him dominant or submissive) and then you should have an option.
This romance is perhaps one of the most unclear, it's on our list for a bit of polish in that regard.