I don’t know what current you want to supply from the +/-20V?
But from a 64V starting point. (i presume its isolated?
Do a buck to give you +20V.
Then do another one the same, but from a different isolated wallwart adapter
Stack their outputs on top of each other…you then have -20v, 0v, +20v.
…You then just arrange FETs to switch between the +20 and -20V at the behest of your microcontroller signal
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alternatively you could do a buck to give you 0-20V, then do a inverting buckboost to give you -20V......then you have your -20/0/+20