A potential difference between two points expresses how strongly charges "want" to move from one point to the other. More precisely, a point of larger repulsion will be associated with a higher potential, whereas a point of smaller repulsion or larger attraction has a lower potential.
And when charges are separated, meaning positive charges are concentrated at one point and negative charges at another point, then the negative ones feel a strong repulsion away from their current position and a strong attraction towards the other point.
Hence, a potential difference between the points. You are right, that such potential difference does correspond to the work that the charge can do, precisely because it will gain the potential energy difference as kinetic energy if released (if allowed to move to the other point), an amount that can then be transfered as work when impacting something else. Equivalently, in order to move a charge away from a point of no repulsion to a point of high repulsion (so moving it to a higher potential), you must supply as work this exact potential energy difference.
A gravitational example might be more intuitive as an analogy: A ball on a shelf will not want to move to another point on the shelf, since the gravitational potential is the same everywhere on the shelf (a difference of zero). But the ball will immediately fall, if allowed, downwards, since lower points are at a lower gravitational potential (the difference is larger). As it falls, all the released potential energy is converted into kinetic energy (speed increases) which can be transferred as work when impacting so thing - to move the ball back up to the shelf, you will have to supply, as work, this exact same energy amount once more.