Since those parameters are very sensitive to the materials' properties, you may provide more details about the specifications of your materials (such as producers, wavelengths interested, temperature, compositions, etc.).
Information of material should be more clearly. Measurement of relative permittivity can be achieved after that relative permeability will be determined.
The measurement method depends on the frequency range you are interested in. In microwave frequency range you can start from the paper by Jerzy Krupka and Adam Abramowicz "Measurements of electromagnetic properties of materials at microwave frequencies" that can be found hete at Researchgate.