Is it possible in SharePoint 2010 to create a Web Application permissions policy that prevents users from accessing a Web Application if they do not have an enterprise license?
If so, how can I create this policy?
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In SharePoint 2010, you cant control this. If user has access to EE enabled Web Application then he will get all services and also count towards the EE cal.
What you can do, create a Web Application and associate EE services(Excel, Power Pivot etc) to it. then create site collection and grant the permission to those user who want to use it. But One thing keep in mind, if site collection admin add a user with read permission will also count towards cal.
In SharePoint 2013, they make it really awesome, you associate the Enterprise Cal to User, so if user trying to access EE site(even having the permission on site) but dont have EE cal associated with his ID then will get error for licensing.