I wrote the latest incarnation of the PETTESTER and I used VICE to test and develop that. I needed it to debug my non-working PET in the first place - and it grew from there!
I use the online assembler at asm80.com. Despite the name, it can assemble 6800 and 6502 code as well as 8080, 8085 and Z80 (and a few more besides).
A 2532 should be a direct replacement for a PET ROM. The 2732 pinout is different and, therefore, requires an adapter.
As Hugo has already stated, the 2532 and 2532A are both OK in the PET - but they do require different programming voltages - so you need to check what your EPROM programmer can handle.
It would appear that the EEPROMs skipped the 2832 variant... They went from 2816 to 2864. Of course, the 2816 is too small (2K) and the 2864 is a 28-pin device - so won't fit in the 24 pin socket (directly)!
It sounds an interesting project - and is what a lot of PETs ended up doing at the time. Not home automation - but in measurement and report production. I used ours at University for controlling an industrial robot for my final year project - but that was many, many years ago when the 8032 was brand new...
Dave