Long time ago, you had to perform "HDD heads parking" procedure, before killing power, in order to prevent heads ramming onto rotating disk surface. Not sure, but i.e. A590 install floppy could still have little utility for that purpose.
Anyway, your SCSI drive, if larger than 300Mb should have autopark actuator servo, meaning you can switch off PSU anytime except while some larger chunk data is being written accross disk (like moving files between disk partitions).
Don't get me literally as a 100% secure source, but somehow I guess GVP should be powered first, before A500. A500 maps GVP RAM in autoconfigured memory address space and that means RAM should be powered before A500 Kickstart routines start. On the second note, powering GVP should spin-up SCSI HDD motor and thus harddrive starts prepared for controller SCSI commands when they start rolling.
Powering off may be in reverse order - first A500, then GVP.
Let's wait for other opinions.