As you have noted in the PingFederate Admin Console, you can specify multiple ACS URLs, however only one is a default URL. Each ACS URL is assigned an index number.
Using IdP-Initiated SSO, the default ACS URL will be used to send the SAML assertion if an ACSIdx query parameter is not supplied. This query parameter specifies which ACS URL is to be used. When the parameter is used, it will send the SAML assertion to the ACS URL associated to the index as shown in the PingFederate Admin Console.
Using SP-Initiated SSO, the ACS URL can be dynamic if the service provider application sends a signed AuthnRequest. Per the SAML specification SP-Initiated SSO can send a ACS URL that will be used by the Identity Provider (in this case the PingFederate IdP) to transmit the SAML assertion. Thus, the requesting server specifies how to return to itself granted the AuthnRequest is signed and trusted by the PingFederate IdP Server.