The scouting party didn't have the Overseer's wife in it, the armoured vault suit I think belonged to Old Lady Palmer's (lady who gave you a sweetroll) Daughter, Anne Palmer, because on the overseers terminal it states so.
Anyway, joining in with everyone else here, James was a doctor and the vault didn't have a docter, so in desperate times, the Vault was opened and even though that goes against the original concept when the experiment with 101 originated, so in order to preserve the better parts of the experiment the Overseer made James and everyone else keep James's inclusion into the vault classified. Which is understandable, when you look at what happened when James left the vault later.
which gets us up to the events of :nuke: :fallout: :nuke: