Hrmm, I generally find steaming spuds takes a little longer - maybe 25mins steaming vs 20mins boiling. Ofc it depends how big they are, if you chop em up, etc. I'm guessing tho steam may be hotter, the heat transfer is perhaps faster with boiling. I dont know, I do find it harder to overcook veg steaming as well.
The water and the steam will be at the same temp (unless you salt the water which raises it's boiling point) at 100C at atmospheric pressure.
The difference in cooking rate is due to the different rates of surface heat transfer between steam and boiling water.
Steam when it condenses onto food transfers heat very rapidly to the surface of the food, many orders of magnitude greater than boiling water. This is why very short contact with steam say from a kettle produces such a rapid and nasty scald compared to boiling water. So, in that case, steam then should cook faster than boiling water then?
Well, yes and no. You see steam will only condense rapidly onto a surface whilst it is much colder than the steam. But as the potato surface warms up the amount of steam condensing reduces significantly ... this is exacerbated by the fact that the potato surface also becomes wet and so steam is now condensing onto the water layer which is less effective surface heat transfer than the turbulent boiling water.
So, in the initial cooking phase, steam is much quicker but at a point it becomes less effective a heat transfer mechanism than boiling water and thus steamed spuds take longer than boiled.