If I understand your question you want a rounded over edge on a box. There are a lot of complicated ways to do it but you could simply use a round over bit. Not just any round over bit. Most round over bits have a bearing. Using a bearing router bit on a CNC is bad. If you could find a round over bit without a bearing, which I think is impossible, you could take a bearing off a round over bit. However most have a stem sticking out that the bearing goes on. That could still potentially cause problems because using a BitSetter would cause the bit to be too high to ever cut the edges. You could compensate for that but it would be some work to figure out how much deeper you would need to set a contour or pocket to compensate for the stem. Also depending on thickness of material you could potentially drag the stem over the spoilboard or material and cause loss of steps.
So if you could get a round over bit with no bearing you could make a custom tool and cut using a contour with no offset to the depth of the round over.
The champher is easier to do with your vee bit but that is an ascetic choice for your design. A round over is possible but problematic.