Even in the case when we are talking about pointing with your finger, there is a difference. Suppose you are standing next to me and I notice a man at some distance pointing TO or AT me. It would not be natural for me to turn to you and say
"Look at that man over there pointing TO me"
although it would not technically be wrong. The natural word to choose would be "AT". The reason it sounds wrong to say "TO" is that when you are speaking, your position is your current frame of reference.
For the same reason, if someone threw a rock in your direction trying to hit you, it would sound strange to say "That person just threw a rock to me".