head to head
Neither is simply harder - they are hard in different places. Cities: Skylines demands more optimization; Portal demands more execution.

Optimization · Pure Optimization
A sandbox city builder that is pure traffic and zoning optimization.

Optimization · Pure Optimization
The portal-gun puzzle game whose solutions are everything.
Cities: Skylines leans Optimization (Pure Optimization); Portal leans Optimization (Pure Optimization).
Portal leans clearly harder on execution.
Cities: Skylines
No reflex demands at all.
Portal
Portal placement timing modest.
Same score on reads - which means the number cannot separate them. The difference is in what each one asks of you.
Cities: Skylines
No adaptive opponent exists in the sandbox.
Portal
No adversary modeling player.
Cities: Skylines leans a little harder on variance, though the gap is small.
Cities: Skylines
Minor disaster events if enabled.
Portal
Deterministic chambers; no randomness.
Cities: Skylines leans clearly harder on optimization.
Cities: Skylines
Traffic flow, zoning, and budgets are fully solvable.
Portal
Pure puzzle-solving optimization.
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.