I fucking love films. I have watched so many over the years! I will list a few that stood out to me for the lead characters. It is as much about the acting by the leads as it is about the film and the characters.
Fight Club (1999) - I'm sure you've seen it but watch it again and study Brad Pitt
Blue Valentine (2010) - The first half of the film when Ryan Gosling picks up Michelle Williams.
Drive (2011) - Another Ryan Gosling film, he is silent and bad ass!
On the Waterfront (1954) - Marlon Brando plays an ex-boxer who plays by his own rules.
The Wild One (1953) - The film is a bit dated but watch it purely for Marlon Brando. His body language is cool as fuck!
Angel Heart (1987) - A mad choice here but your eyes will be fixed to a young and charismatic Mickey Rourke. He is cool and doesn't give a fuck what others think of him.
Get Carter (1971) - Michael Caine plays a calm and composed bad ass out for revenge!
Ipcress File (1965) - A younger Michael Caine as a smooth ladies man, playing a detective.
New York, New York (1977) - A young Robert De Niro is a cocky shit trying to pick up a young Liza Minnelli.
Rebel Without a Cause (1955) - Another film that is dated but keep your eye on James Dean. His cool body language.
Bullit (1968) - Steve McQueen is sooo fucking cool in this. Some hot women in this as well!
The Getaway (1972) - Another one of Steve McQueen films. He takes care of business.
The Hustler (1961) - Paul Newman film. Great acting.
Wall Street (1987) - Haha Michael Douglas is awesome in this!
Harsh Times (2006) - Don't know how Christian Bale does it sometimes! Great acting.
Rodger Dodger (2002) - Campbell Scott teaches Jesse Eisenberg how to pick up women.
Just a list of the top of my head. If I remember any more I will post them. Their is actually a film called 'The Pick-up Artist' with Robert Downey Jr but it isn't really worth watching haha he is a bit needy!