In both methods, it is given that the RDS instance needs a reboot (read as outage!).
In our case, the RDS client application (java-based) had troubles re-establishing JDBC/SSL connection with the rebooted RDS instance (after CA upgrade), so we had to manually trigger a restart of RDS client application to bring the situation to normalcy. Hence, we need to exactly know at what point RDS CA upgrade was complete.
Hence, the workflow would be like this:
1/ Add CA (2019) to your client application's trust store first!
2/ On the RDS side, use 'Apply Immediately' option in lower environments (in Production, we also used 'Apply Immediately' but executed it during the approved maintenance window).
3/ Wait for a few minutes for AWS to apply CA and reboot the RDS instance.
4/ Go and perform post-actions like restart your client application (if needed) and regression tests.
In this way, we were able to limit the outage to a couple of minutes.
Alert: If we would have chosen 'Apply during maintenance window' option, we would not have been 'in control' of at what point AWS would upgrade RDS (CA) because AWS may choose any point in time during the maintenance window specified to perform the upgrade, it is not guaranteed to be at the start of maintenance window.
Hope this helps!