First of all, thanks a lot for the video, this helps immensely in understanding what the issue is!
1. Shoulder Fire:
This is an ADS aim, and with the setup you have in the calculator, 360 distance is not the target for the conversion. Tracking speed is, which is the speed at which you have to move your mouse to track a moving target:
If you want the same 360 distance as hipfire, you need to set the ADS conversion to 360 distance:
2. Ashe vs Marksman Rifle
Again, the conversion is based on the tracking speed of your Overwatch hipfire sensitivity, so it's not expected to have the same 360 distance. Matching 360 distance between hipfire and scopes will in most cases make the scope insanely sensitive and practically impossible to aim with, if not just plain impossible to configure due to the sensitivity range in the game. Also matching 360 distance between scopes in different games makes no sense, as they in most cases will have a completely different FOV. The main goal of a scope sensitivity is to keep the aim the same, i.e. the movement to what you can see on the screen.
You can turn on the advanced mode in the calculator to see the full details of the conversions, where the actual 360 distance is displayed.
I don't know your exact conversion, but if it's something like this: https://www.mouse-sensitivity.com/?share=b18c43ccc759ec230f1ba67d20f8dad8 - then the expected 360 distance for Marksman Rifle in Strinova is 109.5059 cm, while Widowmaker is 125.6535 cm. Since these values are based on the goal of achieving the same tracking speed, doing 360 rotations will only make sense if you use the calculated 360 distance for each scope.