The potential energy of a point charge is just U=qV, where q is the charge on the point charge, and V is the electric potential (as opposed to potential energy, which is U!) that charge is sitting in. And, to find the electric potential, V,(again, not energy) generated by a point charge, it is V = kq/r, where r is the distance from the point charge where you want to find the electric potential.
So, in this case we have 2 point charges, q1 and q2, each of them is sitting in the electric potential created by the other. So, we have q1 sitting in the electric potential created by q2, and vice versa. So let's calculate the potential energy of one of the point charges.
The Electric potential energy of charge q1 is U1=q1V, and V is the electric potential q1 is sitting in, which is created by q2. So V = kq2/r, where r is the distance from q2 to q1. Plugging in we have U1 = kq1q2/r.
And now for the key part. You must put the correct sign in front of the q's! So, we know that in our case one is positive and the other is negative, so what is the sign of the potential energy?
You do the same process for q2 if you like.