The pressure outside a droplet arises from molecules bouncing against the droplet's surface, delivering an inward momentum "kick." Since the droplet doesn't shrink to nothing, there must be an internal pressure at least equal to the outward pressure to provide an equal and opposite momentum kick from internal particle collision with the surface. This provides one term, as mediated by the surrounding pressure.
In addition, there's an energy penalty associated with any surface, as bonds are poorly satisfied at surfaces relative to the bulk. (There are fewer like particles in the vicinity of surfaces.) This energy penalty is equivalent to a driving force for the surface to reduce its area, known as surface tension. This provides the second pressure term, as mediated by the surface tension and the surface area.
The sum of the two terms corresponds to the expression you give in the question.