I assume you have the possibility to synthesize a range of compositions of your material (let´s say AxBx-1, including the extremes). In that case, the information of the diffractograms (d´s and following lattice parameters fitted) should provide the information you require using Vegard´s law (composition vs lattice parameter). This book chapter is a good review, hope you have access Chapter Determination of Composition of Solid Solutions Using X-Ray ...
I would also recommend, whether is possible, to apply others techniques (such as EDS) to cross-check composition of your solid solutions as this is an important parameter to determine for the application of Vegard´s law
In short, a solid solution is formed if there is no phase change from the initial material. From XRD, this is simply indicated by presence of all the same peaks and no new peaks. (Both criteria must be met.)
From XRD, in my view, know the diffracted angle (two theta), lattice distance (d) then solve Bragg's equation to determine the plane (h, k, l). The planes are in proper order for the crystalline structure, if it is formed.
Whether it had been formed crystalline or amorphous structure? You have not reported the materials used to grow as well as the method applied to grow these solids. If you are interested for more experimental work and conclusions, Pl look our publications. Don’t hesitate for query?
For this, I would recommend the latest preprint article at link DOI: 10.13140/RG.2.2.27720.65287/3 or at link https://www.researchgate.net/publication/352830671