What is the difference between µ when being the population mean, and µ when being the mean or the expected value?
What confuses me is that the same letter is being used to describe two different metrics- or are they? I am solely basing this question on their equation which isn't the same, so where am I missing the point?
There is a difference between the population mean and the sample mean.
Suppose you have a population of a hundred birds. The weight of the birds is normally distributed about a mean of 10kg with a standard deviation of 1kg.
Now suppose you take a random sample of these hundred birds, and you select ten. Unfortunately, your random sample was not very representative of the population, and you ended up picking the lighter ones. The weight of the sampled birds is normally distributed about a mean of 8kg with a standard deviation of 1kg.
Thus, the population of birds has a mean of 10kg. But the sample we have taken from the population of birds has a mean of 8kg.
In terms of notation, we usually denote a population mean with $\mu$, and a sample mean with $\bar{x}$.
The expected value is the population mean. See the Wikipedia article, which is quite informative. The idea here is that when you randomly select a sample, you "expect" the mean of the sample to approximate the population mean as the size of the sample becomes arbitrarily large.