Modern digital cross-correlators permit the simultaneous measurement of all four Stokes parameters. However, the results must be calibrated to correct for the polarization transfer function of the receiving system. The transfer function for any device can be expressed by its Mueller matrix. We express the matrix elements in terms of fundamental system parameters that describe the voltage transfer functions (known as the Jones matrix) of the various system devices in physical terms and thus provide a means for comparing with engineering calculations and investigating the effects of design changes. We describe how to determine these parameters with astronomical observations. We illustrate the method by applying it to some of the receivers at the Arecibo Observatory.