Captains
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Captain should be your best player (though I don't think it matters). Pick the best-attacking player (including a midfielder with High Att) to take pens and f-kicks. For corners, I don't think it matters but I personally don't pick a CF (High att low def), and If I know a player who takes corners in real life I pick him. I hope it answers your question.
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I think you have to set as captain a player who is old enough (like 28-34 years old) and the best in his position in squad. In my case, I set as my captain Sergio Ramos, I know he´s a captain in real life, but he matches with the features above: Experient and a good overall (101 def).