I've completed the game with Veronica, Cass, and Boone as well as both Rex and ED-E.
Veronica:
Great for on the Strip work. Give her power armor to keep her alive. For weapons she responds well to Love and Hate and ballistic fists.
Spoiler When you have to confront Benny, she is invaluable. Knocked his ass out before I could take a swing. She also came in handy during the Ultra-Luxe mission of trying to find that bramhin baron's son. When I went to the inspector's room and the guards came, she laid them out.
Cass:
As long as you give her a riot or hunting shotgun with plenty of shells, she is an absolute terror in close range. Probably the best companion to someone who prefers to snipe. If those cazadors get too close, she wastes them with inhuman speed. My only gripe was she would blow through shells like crazy trying to hit enemies that were way beyond the range of her shotgun. As long as you can feed her ammo habit, she is a great pick for tackling vaults nd other close quarters bases.
Oh, I also recommend against using her on hardcoe. I was trying to snipe the deathclaws out of the quarry and next thing I hear was, "I'm gonna six this b****!" She went charging head-on against a pack of deathclaws. Although she did emerge victorious, I think it was pure luck and I doubt that outcome would repeat itself.
Boone:
What's that over there? Oh, Boone already killed it. If you're a melee character that still likes to get out of the house and wander the open expanses of the Mojave, bring a Boone with you. When handed a sniper rifle, Boone will swat anything within 250 yards like a fly. Though not his strong suit, he can still wreck in melee. If you plan to do a lot of melee make sure to give him a rebar club, he seemed to like that one the best of all the melee weapons I gave him (but I never tried the super sledge).
Rex:
Not really worth the amount of work it takes to get him. As others have said, his attacks are mediocre and he dies quickly.
ED-E:
His perception bonus is excellent and he can carry some weight, but the best advantage I found he had was storing my weapons in casinos. On my 2nd play through I found out if I gave my guns to ED-E before I entered a casino, they never searched him and were available anytime I needed them. It's also funny to hear the guards in Gomorra yell, "What the f*** is that thing?!"
Spoiler The 2nd time I played that Ultra-Luxe mission I was planning ahead for those guards that attack you in the inspector's room. I don't think they were ready for an assault carbine loaded with AP rounds.