At high frequencies, when the wavelength is comparable to the size of the component, the phase of voltage and current is not constant along the line or component.These are known as distributed components (coaxial lines,transmission lines, R,L and C at high frequencies).
So S-parameters are basically used to observe the behavior of the components at high frequencies. Where as RLC models hold good only for low frequencies (when wavelength is large compared to the size of the component..lumped component).
So if you are dealing with lumped components use RLC models. If you are dealing with distributed components use S parameter model.