Especially if you're already making enough to get by, the value of the money you're already making is "priced in" to your subconscious analysis. Thus, the next order of magnitude of income really is qualitatively different.
Only if you don't rent a nicer/closer apartment. (OTOH, lower commute times are associated with happiness).
Someone with $100M has access to politics/investments/etc that most people earning $250k/yr don't. So while the average monetary payout is smaller (1% chance at $100M is equal to a 50% chance at 2M), average social currency is much higher. (1% chance at the social power that comes with $100M vs 0% chance in the BigCo job).
Until maybe ~$100M net worth, for me personally, I think an order of magnitude difference would indeed be qualitatively different / better.
There are plausible arguments that money can often have increasing marginal utility for poor people. Google "bee sting theory of poverty".
A 9-5 is unlikely to let you save $1M, much less $5M, unless you're high level in a big company. If you're very early in a big success, you can get there.
However, in many ways, employee 15 and up is the worst of both worlds. Small stock grant, sub market salary and benefits.
Big co: $50k extra from $100k -> $150k = $50k * 1 value / dollar * 100% = 50k value
Startup: $10M extra from $100k -> $10M = $10M * 0.25 value / dollar = 2.5M value * 5% chance of success = 125k value
There's also the intangible value of having hope for big success.