For ideas do a search on Pat Hartman and The Doc Man's posts on designing; by far the best on this site.
For me it's a case of not asking but the person I'm building for showing (not telling) how they currently enact their process. If somebody does this then write it down, and if they do that then make a note (not a mental one) of it. If something gets passed to Jim upstairs then ensure you meet Jim and find out about his involvement, ask him what he does. Make him show (not tell) you what he does. Take notes, and if he then passes info to Sue down in accounts then go meet Sue and get a demonstration. Always let them show you and only ask questions if you don't understand a process (i.e. for clarity).
Eventually, you'll have more questions. Provide a document and return to them and say "is this all you want?" to which they'll say "yes, that's great!"
Once it's complete and delivered they'll ask for thinks they never showed you way back in the early days.