According to Stuff William Shatner would like to be prime minister of Canada. "As Prime Minister I can lead Canada into even greater exploits."Shatner said. I don't know much about Mr. Shatner's politics but I know something of his acting career and so I like to imagine how some of his characters might run Canada.
Captain James Tiberius Kirk - This is almost to easy but it would certainly be entertaining when he punched one of the foreign ambassadors in the face. He would most likely also find a way to spend time with at least one attractive woman on every foreign visit.
T.J. Hooker - I don't know a lot about T.J. Hooker, but as a long time member of the police force I imagine that he would be tough on crime.
The Big Giant Head - Already King of the galaxy he would likely be more hands off than many other world leaders, demanding only alcohol and women in abundance, which makes him not all that different from many earth politicians.
Denny Crane - A legendary litigator in his prime, Denny Crane claims to be the greatest lawyer in history and to have never lost a case. What he has lost, or so it often appears, is his mind. This isn't necessarily a major deterrent to becoming a political leader as he is still charismatic. He is most certainly a conserve, claiming in the past that "Elevators are for Democrats" and only taking the stairs.
Bob Wilson - there's.. something on the wing of the plane (begins sobbing uncontrollably)
I can only hope that he does become Prime Minister of Canada. It would certainly be entertaining.