Hello Shahid,
First off, while the Primary service does not have an IP address, the service name acts as a DNS name, so you should be fine to connect to it. Secondly, even if you did decide to connect directly to the HA service instead of the Primary service, you would not want to use the IP address, as that can change. Again, you'd want to use the DNS name.
So, if both the DNS names for the Primary and HA services resolve to the HA ClusterIP, why should you connect your apps to the Primary service? Well, the short answer is probably "architectural consistency." The HA service exists because we currently use Kubernetes Endpoints for Patroni's DCS. It's possible that this might change in the future and the HA service could go away. The Primary service will exist regardless and will still be the appropriate connection point for your applications.
I hope this helps!
Regards,
Drew