No, you can't just add a fixed amount to a single Settler unit. You CAN change the cost of all settler-type units in your game.
The base Settler's cost depends on two factors: the population of the city that will result from its founding, and the free buildings included in that city.
Specifically, it's all in GlobalDefines:
ADVANCED_START_CITY_COST (84) is the base value.
ADVANCED_START_POPULATION_COST (150) is the amount you pay per extra population. So if you start in a later era, where all cities start at size 3-4, then you're paying 300-450 extra.
NEW_CITY_BUILDING_VALUE_MODIFIER (-60) is the final one that matters. What this says is, if you're in an era where each city starts with a free Monument (cost 40 hammers), add 16 to the cost of the Settler (60% off, hence the -60). Any game where you start in the Medieval or later will have a Monument in every new city. Games starting in the Industrial will have a much larger list of free buildings, which make Settlers in those games extremely expensive.
There's also a small addition for visibility, and they've added an _INCREASE variable to most of these to allow you to make them semi-exponential, but those are the basics.
If you set the Settler's unit Cost to anything other than zero, then it becomes a fixed cost regardless of start era, which can obviously be extremely broken for late-era starts.
Unfortunately, since these scalings are in GlobalDefines, it means that you can't make multiple settler units in a mod, with different power levels and different costs, without making all but one of them a fixed cost. Very annoying.