Hi somnath,
I guess you might want to try directly editing the file src/tools.c.
See line 24 as follows, each number means the order or index of the corr animo acid in "AAs". For example. the first two 13s in line24 means the 1st two codons in the codon table, which are UUU and UUC, correspond to the 13+1=14th amino acid in "AAs" which is F (Phe). Maybe you can either add a new one or directly change an existing that you feel you are never going to use and then re-compile everything. I neither have tried it nor have been involved in developing paml so the above is just my guess. Hope it works.
Best,
Sishuo