The only thing you can do is to change the environment variable of the child process before starting it: it gets the copy of the parent environment, sorry.
This way, you will essentially have a control over the code of the 'getenv' function. Then, you could do all sorts of nasty tricks. Your 'getenv' could consult external config file or SHM segment for alternate values of env vars. Or you could do regexp search/replace on the requested values. Or ...
I can't think of an easy way to do that for arbitrary running processes (even if you are root), short of rewriting dynamic linker (ld-linux.so).
Since the command line is copied into the process’s address space, the process might even write to the memory that holds the command line and modify it. If that happens, then the original command line is lost forever; the only known copy got overwritten.