Hi,
The credentials that you need to enter in the USPS plugin and the credentials that you need to use to log on your USPS account are different credentials. In fact, there is no "username/password" field in the configuration of the USPS plugin but a field called "USPS WebTools User ID" where you need to enter your USPS WebTools User ID that USPS provided you. I encourage you to contact USPS in order to get it if you don't have any yet but normally, you first need to register here:
secure.shippingapis.com/registration/