The actor told TV Guide that viewers will relate to the show's characters as the first season continues.
He said: "When audiences know who those characters are, they want to see how those characters are going to react in a particular situation, and we want to go along with the ride in terms of what they do."
He added that the series will deal with the personal issues that affect his character Cyrus Garza.
"In the pilot, [his father] passes away and there's a guilt factor there," he said. "They were both on a politically different end of the spectrum, and he starts to question where he's coming from."
Smits explained that he had enjoyed playing the conservative Supreme Court justice.
"It's fun to get into the head and mindset of somebody who's not as liberal-minded as I am," he said. "A year and a half ago, I was working on Dexter and there's no way I agree with that character's methodology of how he deals with life on a daily basis. But you find a way [to play it] and make it fun."
Outlaw premieres tonight at 10/9c on NBC. The series will move to Fridays from September 17.