I don't know how to do this with chrome, but you can surely do this within your network settings. Here are a few ideas:
Change Computer Settings: Set your homepage to www.intranet.com (or whatever your intranet site is at work) on both computers. Then on your OS X computer at home, in the hosts file, create an alias for www.intranet.com to direct you to www.superuser.com or wherever you would like.
Change Router Settings: A lot of routers can be configured to this same kind referral.
Set up external website to refer you based on OS or IP: Finally, you could set up your own website www.RickyTheGeek.com that detects your OS or IP and then refers you to one or the other website depending on what it detects.
Create a local file that contains a redirect: On each computer create a local file in the same spot called homepage.html and in each one put 1 of the following 2 lines:
<meta HTTP-EQUIV="REFRESH" content="0; url=http://www.intranet.com">
<meta HTTP-EQUIV="REFRESH" content="0; url=http://www.superuser.com">
Since they are different systems you can't put the full directory name like setting your homepage to
file:///C:/homepage.html, but you should be able to set both homepages to just
file:///homepage.html as long as you can find out which directory each computer looks in when no directory is specified.
So there are 4 options to get you started.