I have five accounts on my PS3, some with lots of DLC, others with not so much, yet all the act.dat files are exactly the same size (4152 bytes), so I think it would be a case of ammending rather than appending. The .rif files are pretty basic.
rif file;
00 00 00 01 00 00 00 02
xx xx xx xx xx xx xx xx (User account)
xx xx xx xx xx xx xx xx (DLC name)
xx xx xx xx xx xx xx xx (DLC name)
xx xx xx xx xx xx xx xx (DLC name)
xx xx xx xx xx xx xx xx (DLC name)
xx xx xx xx xx xx xx xx (DLC name)
xx xx xx xx xx xx xx xx (DLC name)
xx xx xx xx xx xx xx xx (Unknown)
xx xx xx xx xx xx xx xx (Unknown)
xx xx xx xx xx xx xx xx (Unknown)
xx xx xx xx xx xx xx xx (Unknown)
xx xx xx xx xx xx xx xx (Unknown)
00 00 01 xx xx xx xx xx (Unknown)
00 00 00 00 00 00 00 00
xx xx xx xx xx xx xx xx (Unknown)
xx xx xx xx xx xx xx xx (Unknown)
xx xx xx xx xx xx xx xx (Unknown)
xx xx xx xx xx xx xx xx (Unknown)
xx xx xx xx xx xx xx xx (Unknown)
act.dat starts;
00 00 00 01 00 00 00 01
xx xx xx xx xx xx xx xx (User account)