I had never heard of this so I just tried to reproduce this - I have no trouble logging into two separate GitHub accounts in different Chrome profiles. What makes Firefox profiles different?
I think he means when using git from the command line. Trying to push to your repo will trigger a github sign in process, which will then save the credentials to Windows Credential Manager. Git will then ALWAYS use those from that point on credentials unless you go into the manager and delete them, which is a massive pain if you use multiple github accounts.