I generally advise against actively choosing a main, rather than naturally developing one by simply playing it more than anything else, either because you enjoy it the most, or because it is usually your best option in champion select. If you are going to choose one, I would recommend playing one that is not terribly popular, but can do well in most situations. Mastering a champion that other people do not have much experience with can give you a hand up on your opponents, simply because they do not know how to handle you, for lack of knowledge of your strengths and weaknesses. Likewise, mastering a champion who can do well in most any match-up or team composition is a safe strategy, so long as that champion is not frequently banned.