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I was thinking about it for a long time, then I saw this meme and... and it just happened.
Some of these actors were chosen by me because of their acting, some because of facial resemblance.

Here we go:
Sam Worthington as male Shepard, because I hardy think nobody else can portray the savior of the galaxy without making Shepard too hardass or too impersonal.

Jaimie Alexander as female Shepard: I don't care which default appearance was chosen for Femshep, my canon Jane is always a brunette. I think Jaime is incredibly attractive in natural way, in Jane-Shepard-way.

Emma Stone as Liara T'Soni, basically because of facial likeness. I'm kinda in love with both Liara and Emma, and moreover, I think Emma is underrated, acting Liara could change that for sure.

Seth Green as Jeff Moreau: Joker isn't Joker if they'd gave him another voice. Also, just look at this guy!

Yvonne Strahovski as Miranda Lawson: please. Yvonne IS Miranda Lawson.

Eric Bana as Thane Krios: I'm not completely sure about this, I never really liked Thane (sorry ~mappeli!, but I would definitely liked him portrayed by Eric Bana.

Michael Trevino as Kaidan Alenko: many people agrue with me about this one, but when I first saw Kaidan I nearly choked and first thought about Michael. He is probably too young to play Kaidan (27y/o) but maybe someday, somehow.

Michelle Trachtenberg as Tali'Zorah: I always thought that Tali looks something close to Michelle. Also, despite everyone's opinion, I think Trachtenberg is a good actress.

Tony Todd as David Anderson: choice is based on their likeness, aaand... and that's it.

Sterling K. Brown as Jacob Taylor: Sterling is also known as Gordon Walker on Supernatural, and I must say I was impressed with his acting. I'm not sure how good he is at good guy roles, though.

Lena Headey as Samara: Lena as Cersei in Game of Thrones is something. I think she's got that powerful justicar charisma.

Genevieve Padalecki as Ashley Williams: first I thought of Zoe Saldana and Michelle Rodriguez, but then I remembered this woman. She fits just fine.

Michael Fassbender as Garrus Vakarian: mostly because of his magnificent blue eyes. I have an enormous crush on both Garrus and Michael, so there was no doubt for me.

Gary Oldman as The Illusive Man: I adore Gary Oldman, though he is more known for playing good guys, I first thought of him when I started searching for an actor for Illusive Man.

Mila Kunis as Jack: Mila's sexy just like Jack, and her husky voice fits Jack, too. Anyway, Megan Fox is also an option.

and David Tennant as Mordin Solus: David can play anyone, or anything, he's extremely good in about any role. He would be a true Mordin for sure.

Whew, that was my longest description