When interviewing senior people, I like to get them going on war stories. "Can you talk about a project you experienced that went very badly?" is a good one. It's not necessarily that they went badly, but we've all been on death marches before (and I absolutely would not hire an architect who's never done a death march!).
The beauty of this is you can find out how they react to impossible demands and pressures. What they're proud of accomplishing in dire circumstances. Possibly what they're ashamed or embarrassed about, or mistakes/lessons learned (if they're that bold). You can learn a ton about how they talk about their colleagues! Are they full of praise, or contempt? Do they find someone to blame, or talk about how someone else saved their asses? You can also learn a lot about their actual approach to technical decisions - their taste, for lack of a better word.
You can ask probing questions here, but the important part is to get them speaking in an unguarded way. Nobody makes it to the architect level in this field without at least kind of loving the job. Find out what they love. Find out what they hate. Find out what they regret. Find out any strong technical biases they have, and why. But most of all, find out how they play with others. Because the architect's job isn't just to design, but to communicate. You don't just want a technical expert. You want someone that can value and respect the rest of the team, or they're just going to cause problems.