I think we've figured it out. Along the lines of Landing Gear's suggestion, we installed this add on to his Outlook software, then set up Outlook to show his Hotmail account.

In Outlook, copied his calendar from his work account to his personal account. Will do the same with other key files (contacts, personal email on work account) and make sure it's all synced to Outlook.com before removing the personal account from the Outlook software. (Right now it says its syncing, but haven't seen the changes appear on Outlook.com yet.) At least then we have it all in Hotmail/Outlook.com...

I'm still a bit iffy on the iPhone stuff, but I assume we can use iPhone's native email client to read Hotmail/Outlook.com mail, right? Can iCloud be synced to a Hotmail calendar or does he need a different calendar app?