Pay as you go is just like it says, you pay for only the services that you use, based on the pricing for that service. More info here.
A subscription is as described here "a logical grouping of Azure services that is linked to an Azure account. A single Azure account can contain multiple subscriptions. Billing for Azure services is done on a per-subscription basis. For a list of the available subscription offers by type, see Microsoft Azure Offer Details"
You have two subscriptions set up. On is a pay as you go subscription, and one is another type, although I'm not sure what. There should be no difference which one you select from a technical standpoint. It is only a matter of how you want to be billed. Azure web apps have a free tier as well.