For DoA I think it's gotta be Dante and Sanguinor.
Dante allowing you deep strike melta guns with 100% accuracy is a tool you can depend on, and he adds an extra melta gun to the squad which has nice synergy. I think allowing you to take Sanguinary Guard as troops is what really sells him. SG are a nice unit, but not one I would be happy burning an elite slot on. As troops however they are almost irresistible.
Sanguinor is just a beastly CC beast. Adding +1 attack to nearby assault squads is a great force multiplier, and his blessing basically gives you an extra character for free.
For Mech BA I would say Mephiston stands out the most. Tycho gives your entire army Ld 10 for morale and pinning tests so I would pick him for #2.
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