First, know what you're looking for. Everyone has important things and papers in their space. But, not everyone keeps them in an organized manner. Keep your eyes open for birth certificates, deeds to property, passports, account numbers and the like. These documents will be necessary for the estate executor to carry out their duties. Important finds also include credit cards and keys (to the house, the car, the lock box...).

Third, know when to call in another expert. If you come across items that appear to be rare or of particular value, call in an expert. Antique dealers, jewelry appraisers and even local historians can be of help. Sometimes, we find items that are so old or rare that we don't even know what they are. Online research can at least provide a starting point.
And lastly, know when you're done. If everyone has found the items they were intending to claim, and all sale-worthy items have been sold, it's likely time to start bagging up donations. Donate anything else left in the home that can still be used by someone else. Consider finding a charity with which the deceased was a part or supported, if possible. It can often make the process a little easier knowing that someone else can find use and joy from the items that remain.