If the players in a Texas Hold-em are fairly evenly matched then it is as much luck as anything, and no matter how good anyone is nobody would win every time, or even most of the time. Overall I would give this one to Spiderman. This is my guess at the average winning percentages and my reasoning:
Spiderman - 30% - He is the only one with any form of precognition, and that is a massive advantage. His weakness is that it won't help him much until the final card, so he takes a risk when he stays in a big hand without knowing how it will turn out. But he is smart enough (has collaborated with Reed Richards, and added value!) to play the odds very well to keep him in the game until his spider sense kicks in to give him a huge advantage.
Daredevil - 25% - Can't be bluffed, at all. This will get him to the final two in most games. But then it becomes mostly luck, and he will only win half the time.
Midnighter - 20% - He will play the odds the best so he will win fairly often.
Batman - 15% - He is smart enough to play the odds well, and his detective and people-reading skills will help out with detecting bluffs.
Deathstroke - 10% - I use 100% of my brain, as do almost all of us, so using 90% means he is mentally deficient.... But I know what the writers are trying to say, so I will treat him as being very smart. So basically this guy is smart enough to compete well, but he really has no special abilities that help in gambling aside from being smart. But just being smart at a table full of smart people who also have special abilities to help them leaves you at a severe disadvantage.
As to actual combat, Midnighter wins since he has the best overall combat superpowers and skills. Spiderman second, then Batman or Deathstroke (toss up), and finally Daredevil.
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