XRR reflectivity can measure the thickness but it has to be used with a caution. Unless your film is a single layer, you'll have to model XRR response to match your experimental data to deduce the film thickness.
As others mentioned, there are other profiling techniques which you can utilize such as cross-sectional SEM, cross-sectional TEM, AFM (if you film is very thin, within a few nm), optical profilometers, spectroscopic ellipsometry, and profilometers with physical stylus (e.g: Veeco Dektak lines).
All these techniques have their pros and cons thus it all comes down to what technique will suit your film the best (as other have mentioned above).
In principle, specular XRR and XRD are actually same. Both can get Bragg pattern of your film (if your sample is sort of lamella structure like mine), and refine the data by means of form factor, thickness. Form factor magnitude can be estimated from the reflected intensity and qz (angle). The point is you should be aware of your sample structure to design the fitting routine.
XRR is the general term used for measuring thickness of films ranging from amorphous to crystalline to epitaxial. The measurements are generally made by examining the long range order signal close to the I0 (incident beam vector). Correct? XRR, SAXS, GIXRD, WAXS etc. fall in to the super set of XRD, I'd think.
Please review the following post for super lattice epitaxial film thickness and make suggestions when convenient.