the capacity is the capacity, a 4500ma capacity is less than a 5000ma capacity, no mater the package size.
although
If its in a larger package (D vrses C) and of similar capacity, then chances are it might be more "robust"
in other words i would rather have a Ni-Cad cell of D size and 4500ma , than a High cap C cell ni-mhy of 4500ma, because it might cope with more issues. or say a new tech LSD D-cell of lesser capacity than a high-cap C cell of normal ni-mhy.
soo i would never (well almost never) waste the space of a D-cell location with a C-cell of even greater capacity, because the more materials in the D-cell could be materials that make it more robust, and long lasting. if you have the SPACE and can handle the weight of the larger cell, and everything else is the same (including cell quality) then use the D-cell.
this of course discludes stupid "sleeved" batteries that have no more battery materials, and are just plastic spacers.