Here i have attached a link, which will explain the basic things u need to understand in doing Rietveld refinement and also have a practical tutorial attached with it . Go through the tutorial. This is based on a software package, GSAS.
This is a classical one million dollar question! You must start to use the tutorial that many softwares have. You can try Fullprof, Gsas, Maud and others. But also if the refinement seems a simple tool, pay attention to the results interpretation
I recommend Full Prof Suite, i think the interface is friendly. I have made refinements of structures known in contrast to the same with any modification, so:
1. Translate your experimental dxr file to a format to be read in full prof.
2. Find the cell parameters in programs like Find it.
3. Use the tutorial to build the file to refine.
* I know how to refine, so these are the minimun things you have to be clear.