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Along the baselines inside.
If you stay after the game, go down the street along the 1st base line toward the outfield gate. You will see a long curved stretch of movable metal barriers where people can stand. If a player wants to sign he will come out the garage door in the stadium and pull up along the barrior somewhere and sign from inside his car.
Occasionally, as traffic can get bad along Mazeroski way, players can get stuck trying to enter the traffic about halfway between homeplate and some will sign there while waiting to move. Others will ignore you.
I did PNC post game for the first time in May. After the Friday game I got Andrew McCutchen, Charlie Morton and Jeff Karstens down near the traffic. No one pulled off to sign in the first area I described. After the Saturday game, Cedeno signed near the traffic and Charlie Morton and Pedro Alvarez pulled up along the barriors and signed.
If your going for the opposing team, you will have to do it inside the stadium. The players board a bus under the stadium and pull straight into traffic. You will never see them.