I'm not an expert in ISA Server at all, but i'd suggest you use the wizards to setup your rules.
We've used subdomains/ip addresses to split the portal and mysites, which are then directed to the appropriate server/port.
So:
portal.demo.co.uk -> dev:701
mysite.demo.co.uk -> dev:702
Thus the order of these rules is not important, as they are quite different.
We use different listeners for internal/external, so we use 4 rules for this.