The purpose of the boot-time scan is to deal with any issue which the regular avast scan can't deal with.
This is typically when a file is detected as infected and avast can't move it to the chest because it is protected or in use, by scanning outside of windows it is unlikely to be either protected or in use so can be detected and moved to the chest.
If you get a virus in memory avast also suggests (offers it as an option) you do a boot-time scan.
If you suspect something out of the ordinary is going with your system, again try a boot-time scan, but it isn't something you need to do on a regular basis. That is the preserve of the Simple User Interface on-demand scan where you can be a little more selective on what is scanned (area, with or without archives) and to what degree (sensitivity).
How long do regular on-demand scans take, assuming you do any ?