All working now, but I've had to do almost all of the suggested "fixes" mentioned in this admittedly quite helpful forum. So to recap:
Vista 32bit VS2010 Pro. Attempting to run the sample app in "local" mode using the Azure emulators.
1) The dependency checker incorrectly said .NET WCF ACTIVATION was inactive. I right clicked to skip this dependency.
2) Noticed the Azure compute emulator had bumped the service to Port 444. Using a great little utility called CURRPORTS, I, like others, discovered Skype was hogging 443.
3) Turned on HTTP redirection.
4) Deleted the user file in the application directory.
It does take around 10 minutes to start after hitting F5, and it does bring my dev machine to its knees. I'm guessing the Azure emulators are quite hungry? Time to get my Azure account.