Just be a bit careful when exploring buildings next to Rivet City or in the far west of the map. By exploring a certain garage and the Jefferson Memorial, you might accidentally skip ahead in the main quest and lose some quest reward XP.
One hint though: if you are keen on, let's say, a greater variety of foes out there in the wasteland, then you might want to consider finishing The Waters of Life at some point though, before you've explored every nook and cranny.
You fight a lot enclave soldiers, ghouls and mutants during waters of life right? Any case, i am keen on engaging great variety foes. I got charon and dogmeat to back me up. I equipped charom with lucky shades, terribe shotgun, victory rifle, railway rifle and a sheesh kebab and set him to flank. Signed for Crowley's quest and got the ol' painless rifle. Rosie is now president of the republic of dave. hehhe Now, i need to complete reilly's rangers quest to avail better armor for charon. This game is enormous. Right now, i'm still disovering new locations and have only maxed out my energy and small guns skills.