The statistical definition of "population" means the group being surveyed, while the actual surveyed PCs would be the "sample group." So you can be part of the population (Steam users in a given month) and rarely if ever get sampled. Generally speaking, even if you only sample less than 1% of the total population, if the sampling is truly random you end up with reasonably consistent data. The margin of error and confidence level would change based on how much of the population you sample. If you sample 100%, you have a 0% margin of error and 100% confidence level. If you only sample 1%, it will drop quite a bit to maybe something like a 3% margin of error and 95% confidence level.
But as I said before, we don't know the population size, and we don't know how many PCs/users are sampled, which means we can't determine the margin of error at all. Valve could, yet it chooses not to, which has always struck me as rather odd. I mean, go look at BackBlaze's HDD reliability statistics. That's REAL statistical analysis, and you could pretty much automate the whole thing with Steam so that it would generate the monthly pages and have a short sentence at the end saying, "Steam sampled XXX PCs out of a population of YYY, giving a margin of error of ZZZ% and a WWW% confidence level."
Which is probably the main reason Valve doesn't do exactly that: It doesn't want to give a truly hard piece of data on how large the population is. But Valve does release a statement every couple of years about how many Steam users there are, peak concurrents is always given, and stuff like that. And Valve doesn't actually need to provide people with any data at all, so it's kind of cool that it chooses to at least give us some insight. But if you're going to periodically list user base and if you gave a monthly summary of the user statistics, we'd undoubtedly have others writing, "OMG, Steam is imploding because there were 5 million fewer users this month than last month!" And then the next month: "OMG, Steam had its best month ever with 10 million more users than the previous month!"
So in summary, I bet Valve is doing reasonably proper statistical methods, and the only reason it doesn't provide more insight is because doing so would allow people to work out how large the "Steam Population" is every month, and it doesn't want to provide that data.