Nothing wrong in what you're doing. You cannot see that LightOrange
variable value what you're setting in OnStart
under Variables
area like debug mode.
I'm seeing arunColor
variable with No value
.

I'm assigning #0000ff
(Blue) using Set
from App OnStart

I'm assigning that variable value arunColor
as control color Fill

I'll use one of these urls to access the App after save & publish.
https://apps.powerapps.com/play/d68b7936-xxxx-xxxx-xxxx-ce064e3f1637
https://apps.powerapps.com/play/d68b7936-xxxx-xxxx-xxxx-ce064e3f1637?tenantId=e485c427-xxxx-xxxx-xxxx-add2e5942a49
Voila! I see the control color changed.

Reason:
OnStart
is designed to trigger when the app is opened very first time. If you make changes in color, then you have to open the App again to see the changes.