Electric Potential Energy, like any other potential energy, is defined in relation to a conservative force: in this case, the electrostatic force. If one moves a charge from one point to another through an electric field, one must exert a force over this distance... hence work has been done, which corresponds to a difference in the potential energy.
The electric PE at a given point is generally defined relative to a point at infinity; ie. infinitely far away from the influence of any other charges. This is why we talk about "bringing charges in from infinity" to calculate the potential energy of an arrangement of charges.
One additional complication with electric potential energy compared to graviational potential energy is that charges have different signs. That means that the forces which lead to the potential energy can be either attractive or repulsive. It is perhaps worth drawing from the vector definintion of work:
which tells us that we consider only the contributions of the force which are parallel (or antiparallel) to the path. The result? If we are moving the particle on a path parallel to the force on that particle (the force is acting in the same direction we are moving the particle), the work done by the force will be positive, and the potential energy will decrease. Since we are starting at infinity where the PE is zero, this means we will end up with a negative PE. Conversely, if we are moving the particle in countering the force (the force and direction are anti-parallel) then the resulting PE will be positive.
In this way we can think of PE around charges as hills and valleys: if the force between the "active" particle and another in the arrangement is attractive we will have a potential energy valley, but if the force is repulsive we have a potential energy hill. Let's hold onto this landscape idea and revisit it in relation to electric potential.
Electric, or electrostatic, Potential is the electrostatic potential per unit charge. Think of it as: electric potiential is to electrostatic PE, as electric field is to electrostatic force. That means that the electric potential takes on all the same characteristics as the electrostatic potential: it is a scalar quantity, it can be positive or negative depending on whether the interaction is repulsive or attractive.
Like the electric field, the sign will be determined by considering a positive test charge. With electric field, the direction of the vector quantity is determined by the direction of a force on a positive test charge. Since electric potential doesn't have a direction, it is just the sign which is determined by the positive test charge.
Let's return to our landscape idea then... with PE, we have to consider the magnitude and sign of the charge we are describing, however, since electric potential is per unit charge, it will always remain the same (unless the charges defining the landscape move). Since the positive test charge will be attracted by negative charges, there will be "valleys", or regions of negative potential near these, and near positive charges there will be "hills", or regions of positive potential. In this way, electric potential is kind of a measure of the attractiveness and repulsiveness of a position... just remember that it will be opposite for a negative charge.
I hope I've helped, and not muddled the situation further. Please post a comment if you wish some clarification.
I have some other resources posted for you on the topic of electric potential and potential energy for further reading:
