Yes, we keep a pricebook. I have a detailed excel workbook on my computer where I record the average price of a good and number of purchases of that good included in the average (sometimes broken down by brand depending on whether I'm very specific with that item or not), along with the lowest price I've paid, the location I received that price, and what the circumstances were (sale, new brand, coupon, etc.). I dump the average prices to another worksheet about once a month so I can see how prices on some items are tracking over time.
For hitting the stores, I carry a $1 address book with me. I have the goods written out as contacts (milk under M, for example, it makes it a quick look up). Before I leave, I pencil in the latest average price and the lowest I've received. When I think about it, I jot down any prices I see on the third line in order to keep my averages up-to-date even if I'm not buying that item today. When I print my grocery list, I look over sales, circulars, and coupons to spot any exceptional deals available (most of the time, I simply note that the "sales" don't beat average prices and the coupons don't bring the name brand item down to the price of their competitor).
For fun, I'm doing a commodity basket pricebook in the winter months. The idea is that you come up with an "average" grocery list and you compare multiple stores on the same items. I'll probably set it up to compare it either seasonally or longitudinally over the course of a year, once a month wise.
No one needs to get this intense about their pricebooking. For me, it's a hobby. I pricebook more than just groceries, I pricebook clothing, furniture, electronics, and even whole vacations. What I've found is that sales and circulars are rarely indications of a good deal and "general" discounters are rarely cheaper than their competition. The same things tend to go on comparable sale at all the stores in an area, so it gives the impression of a bunch of gas stations with the same price per gallon. You can get good reliable deals at brand specific grocery outlets, such as $1 cakes at the Pepperidge Farm outlet maybe once every other month, with no limits on stocking up.