When doing measurements on substrate material candidates one is usually going for low loss type of dielectrics .And in this case the waveguide resonator has a higher sensitivity compared to microstrip/stripline but is also narrow band. "Microstrip antenna method" you should define. There are MANY ways to measure substrate materials with microstrip and also stripline techniques.
Note too that there are also coaxial waveguide techniques, and various variants including open ended waveguide (reflective) and both internal and interface techniques. In the internal, for either rectangular or coaxial waveguide, you cut a sample to fit the waveguide. However, the fit of the sample can have a drastic impact on results since a small air gap can dominate and compressing the material can change its properties. For relatively thin sheets, two open ended waveguides can be used to sandwich the sample, but that has limitations and caveats as well.