head to head
Neither is simply harder - they are hard in different places. Fallout: New Vegas demands more execution; SpaceChem demands more optimization.

Optimization · Pure Optimization
A faction-driven RPG-shooter where build and route planning shape every ending.

Optimization · Pure Optimization
A hardcore programming-in-disguise puzzle where you wire atomic assembly lines to synthesize compounds.
Fallout: New Vegas leans Optimization (Pure Optimization); SpaceChem leans Optimization (Pure Optimization).
Fallout: New Vegas leans clearly harder on execution.
Fallout: New Vegas
Shooter inputs with VATS assist
SpaceChem
Drawing waldo paths requires no physical precision
Fallout: New Vegas leans a little harder on reads, though the gap is small.
Fallout: New Vegas
Scripted factions and enemies
SpaceChem
No opponent; pure logic construction
Fallout: New Vegas leans clearly harder on variance.
Fallout: New Vegas
Some loot and crit RNG
SpaceChem
All reactor inputs are deterministic and fixed
SpaceChem leans clearly harder on optimization.
Fallout: New Vegas
Faction routing, perks, builds heavily rewarded
SpaceChem
Designing correct chemical pipelines that transform inputs to outputs exactly
A matching score does not mean a matching test. Two games can both sit at 10 on execution and demand completely different things of you - which is why the reasoning above matters more than the number beside it.