Your reasons are your own and no one here will question why you need something, but will try to help you get there... lol, well, we will try to help anyway...
Sure you can. Do you want to do this switch manually or remotely (from a dash toggle switch)?
Look up solenoid switches. With these you can use a little dinky dash mounted toggle switch to power a bigger high amperage switch that carries your charging current.
There may be what you are looking for, but if not, you can get a toggle switch and two 20+amp relay switches. I know the smaller relays have Normally Open (off) and Normally Closed (on) options, but not sure about the big solenoid switches. It will say NO for Normally Open, NC for closed.
You wire it to NO or NC depending how you want the relay to work.
NO means that when the little toggle is not giving it 12v power that the solenoid is off and not letting current run. Wire each differently and when little toggle is off for NC version then power will flow through the big relay. So, wire both big relays to the one toggle. When toggle sends power, one big relay will be off and one on, because when one gets power it lets current flow but does NOT let power flow when it loses power.
Opposite for the other way, when it does not get power it lets current flow, but when it gets power it stops current from flowing.
So, if you have one of each set-up then you can send power to both and one will work, one will not, Stop power and one will not work, one will work.
This way only one set of batteries is connected to your charger. This happens on the positive wire side only of course.
Now, this is exactly how relays work, and relays are all over your vehicle and just look up how to wire them online rather than me butcher it.
Maybe you can get a relay that will take your 20 amps, or maybe you need get a big solenoid to do the 20 amps.
I just have not played with or know of a big solenoid that has options for Normally open/closed, but relays do have this...
Big solenoid ones:
Little Relay switches:
Actually, the middle bottom one looks like exactly what you need, already set up and described in picture for you. I got these pics off internet search results.