The complex frequency variable s=sigma+jw is used primarily to compute and to describe some specific properties of the network (pole and zero location in the complex frequency plane).
More than that, the denominator of the transfer function - if expressed using s - is identical to the characteristic polynomial of the corresponding differential equation in the time domain.
This clearly demonstrates the relation between time and frequency domain - and, thus, justifies the usage of s.
However, when you try to measure or to calculate the real frequency response (magnitude and/or phase) you must use the "physical" frequency w=2*Pi*f because the complex variable s is only for mathematical purposes and cannot be generated as a test signal.