The standard entropy of a substance (at 25 C then) is measured by determining the amount of heat required to raise the temperature of one mole of substance by 1 degree K.
Where did you get that from? Just because they both have units of J/(mol K) doesn't mean they are the same thing.
The relation between them is dS/dT = C
p/T
S increases with temperature. C
p, to a first approximation, is usually fairly constant over a limited temperature range. The fact that your values of 75.3 and 69.6 are quite close is coincidental; change the temperature significantly and the entropy value will be quite different.
Moreover, the value of standard entropy depends on the standard state it's relative to. For example, though this page
https://en.wikipedia.org/wiki/Water_(data_page) says the standard molar entropy is 69.95 J/(mol K), the data table 2/3 way down the page gives S at 25°C = 0.367 kJ/(kg K) = 6.61 J/(mol K), relative to S
liq = 0 at 0.01°C (triple point temp). What is the reference state for the 69.95 value? S
ice = 0 at 0K? They don't say.