The best way to think of the Schedule items is this: "On this day, at this time, set the Send Push Notifications and Record Motion Events checkboxes to this state"
For example: If you want to turn Push Notifications on every day at 8 am and off at 5 pm but Record Motion Events all the time, create one item for Every Day at 8 am that has both checkboxes ON and another item for Every Day at 5 pm that has the Record Motion Events checkbox ON and the Send Push Notifications checkbox OFF.
If you wanted to turn the Recording of Motion Events off as well, you just need to uncheck the appropriate checkbox in the second schedule item.
Hopefully that makes sense.