The start and end times are the window in which the cron schedule is active. They do not specify the first and final time a trigger will be fired.
For example a schedule that fires every hour with a start time of 9:30am and end time of 6:30pm will fire on the hour during this period.
In your case this is not relevant as your cron schedule is once per day at 10am and this falls within the start and end time window.
If you want to fire a job at both 9:30am and 10am each day then the easiest way is to create two cron triggers that both invoke the same job.