I would have to say that it would be extremely difficult for you to estimate the relative quantities of coins in circulation through any but an exhaustive (collecting a large portion of those coins simultaneously) survey.
The reason is because most businesses (I believe) hold a reasonably large portion of coins in stock and will only distribute the coins which most efficiently lead to correct change. Thus even if you go into the same store 100 times and collect change each time unless you have exhausted the stock of available coins, the coins that you receive in exchange for your sampling will only be those which correspond only with the least change required to fulfill your needs.
Assuming you draw change requirements uniformly between 1 cent and 499 cents this ratio is:
200 100 25 10 5 1
0.13559322 0.06779661 0.25423729 0.13559322 0.06779661 0.33898305
If the store has no shortage of coins then your sampling procedure will automatically return the above ratios which have no correlation between the specific samples and the greater population of coins in circulation. To see how I came up with these numbers see my blog post on the topic.
But this does not account for the oddities of prices which tend to cluster ending in .09 as in .99, .49, or .39 (in the US at least) which will definitely contribute to higher ratio of pennies required for many purchases than in the uniform draw of change. Purchase requirements would need be specified so as to not cause further contamination of the data. Overall, I think it is clear that this is a pretty problematic study design.
If you were forced to do something like this then you might be alt to 1. record change totals for each purchase, 2. calculating efficient coinage selection via the method I propose on my blog for each purchase, 3. record coins actually returned, 4. estimate the different between the optimal returned coin quantities and that actually returned to estimate to what degree coin stocks might be diverging from the optimal quantities. From there I am not sure what to do with it in order to estimate total coins available in the currency.
Good luck and thanks for the interesting question!