There are a small handful of powers that work really well outside of combat - perhaps even better! - as well as within it. Mostly utilities, of course. One that comes to me immediately is the Avenger's Oath of the Relentless Hunter that lets you determine distance and direction to a target, even across planes to some extent! A sampling of others by class in the PHB1:
Cleric - Cloud Chariot, Angel of the Eleven Winds
Fighter - Get Over Here, Come and Get It
Paladin - Astral Speech, Angelic Rescue
Ranger - Crucial Advice, Undaunted Stride, Longstrider
Rogue - (most of them - the Rogue really shines here)
Warlock - Beguiling Tongue, Shadow Veil, Fey Switch
Wizard - (again, most - keeping pace with the Rogue)
The majority of them involve moving/flying/teleporting. Some give bonuses to skill rolls and a few - primarily the wizard's - just do neat things. I'd like to see more in this latter category. Perhaps something like..
Oh, You Mean THIS Key?
Daily, Free * Martial
Prerequisite: 13 Dex, must be trained in Theivery
Effect: When you use this power, you reveal a small, non-unique item that you pilfered from an NPC. The item is determined when the power is used, not at the time the pickpocketing would have taken place.
Encourage your players to take utility powers that don't give bonuses - or do so to skill rolls - if you want to see powers used outside of combat. Also consider making rituals more plentiful and possibly quicker to cast.