Now, will this have a lot of buffer overflow errors on a 486DX-33, or is that slow enough where it won't be much of a problem? (mainly going to be playing Sierra games on the PC)
Sierra games should be fine on systems of
any speed if your ISA bus speed is correct --- Cloudschatze and I have found that this is too often not the case. Just try it and see if you get any error messages.

You'll definitely have problems with LucasArts games though.
Should I get another interface card, or run it through the MIDI THRU on the MT-32, or something else?
A seperate inferface card is only necessary if you want to control the MT-32 independently from the SC-55, for example if you use both for composing. If you'll only be using one at a time, connecting them via MIDI THRU and turning down the volume of the other, unused, module is probably the easiest and cheapest approach.