Looks like the easiest way to do this is find an e-mail from the contact with the digital signature on it. The contact's name should have a crest beside it. Clicking on the crest lets you see the certificate, where you can remove it and untrust it. This seemed to sync between my iOS devices, but I'm not sure.
If you do not have a signed e-mail, I don't know how you can do it. Removing the contact, and removing the address from previous recipients did not work as e-mails are encrypted again when I use the same destination address. You can, however, stop encrypting all e-mails by going into Settings > Mail, Contacts, Calendars > Accounts: your@account > Account: your@account > Advanced: Mail: your@account > Advanced > S/MIME: Encrypt > No. You'll also find your personal signing certificates here.