They can’t, unless qmail has been configured to know they control mail for domain.tld. The admin configuration mechanism for this (control/virtualdomains) is simple and powerful.
Sorry I'm confused. If your mail server is setup for control of a domain (e.g. domain.tld), then what stops someone from putting postmaster@domain.tld in this .qmail file?
People can put whatever they want in their own .qmail files. That doesn't affect anything unless qmail believes those .qmail files are relevant to what it's delivering. A user controls .qmail files for a domain if and only if an admin has configured qmail to delegate that domain to that user.