I'll assume your MX records are only pointing to Postini. In your
admin console for Gmail, under Service Settings -> Email, make sure
you have the outbound settings correct.
Next, add in the Postini IP in the Inbound Gateway section, also
checking the box, "Only let my users receive email from the email
gateways listed above. All other mail will be rejected."
Postini IP's are
64.18.0.0/20 for System 7 and
207.126.144.0/20 for
System 200. The number in your Postini record will tell you what the
system number is.