For each escalation schedule - you can add exceptions.
For example, I went into my Incident - Response Escalation schedule.
I've highlighted my Data Service schedule.
Then I click "Set Exceptions"
Here I can pick a value to set my exception for.
I've selected Owner as the field
and I want Administrator Admin to have a different escalation schedule then the rest of my team.
Now highlight your new exception.
Click "Set Thresholds"
Here, you can set the business hours and escalation levels.
Click OK after changing your HOP and Escalation Levels.
This will allow certain users to use a different schedule than others BUT within the same Escalation Schedule. This especially helps for teams that are split up in different timezones.
You can use different fields to differentiate, Owner is just an example.