VOF and SIMPLE are two different issues in CFD (oranges and apples not comparable!)
VOF: Volume of fluid method for tracking [sharp] fronts of free surface or surface of two non-mixable fluids, the method is developed by C. W. Hirt in Los Alamos. In that line, there is other method which is called Level Set Method, developed by Osher, S.; Sethian, J. A.
SIMPLE: is a method of efficiently solving Navier-Stokes equations by B. Spalding and Suhash Ptankar, there are many modifications to that like, SIMPLER, ....
The second very most common way of solving N-S equations is Chorin's Projection Method
[Back then it was fuzzy, I think you reword that anyway:]
VOF defines the domain boundary, based on the values it get from SIMPLE solver (or any other N-S solver) then within that domain N-S is solved. They can be one-way or twp way coupled based on how sharp the free boundary changes