I think, as in most GROMACS tools, the -n option and an index file containing the indices of the atoms of your amino acids with the proper selection of groups should do. Be sure to choose and carry out an apropriate fitting method before doing the RMSD (e.g. fit this residue, backbone only or whatever fits your purpose the most).
RMSD is easily accomplished using one or other of the various molecular graphics tools. I would recommend YASARA which has several methods for doing this. My own preference among these is the Sheba superposition tool.