It can either align with the official calendar (groupBy values of "Day", "Week", etc.) or with the custom time cells. There is no way to change the week start to a specific hour of day (in the headers).
I find this kind of cell arrangement a bit confusing. The cell start doesn't really mean anything.
I would recommend a different approach: Make the first timeline cell partial (starting at current time and ending at midnight) and use "width" property to make it proportionally narrower, then continue with standard days starting and ending at midnight. The last cell can also be partial, starting at midnight and ending at the current time.
This way it will be obvious that the Scheduler displays just a part of the first and last day while the other cells will be standard.