Early Stamps
With the Penny Black, Great Britain was the first country to introduce stamps in 1840. The U.S. released its 5-cent Benjamin Franklin and 10-cent George Washington stamps seven years later. Stamps dating from the first 10 years of philately after 1840 can be easily spotted because they lack perforations, which were only introduced in the early 1850s. Before then, the postmaster would have to cut or tear a stamp from a large printed sheet.
Denominations
A stamp's denomination is its printed face value. The higher the denomination, the fewer were originally made. This impacts on rarity and thus on the stamp's later value on the collecting market. Bear inflation in mind -- a U.S. stamp from the 1890s bearing a denomination of $5 represents what was once a very considerable sum. Nor should one forget that modern unused stamps of a high denomination have a value as legal tender within their country of origin.
Collectible Countries
In philately, not all nations are equal. Largely because of strong followings in their own countries, British and American stamps are the most collectible, followed by America's dependencies and the countries of the Commonwealth. Even with these countries, stamps dating from after World War II are usually modestly priced. When buying a stamp album, check the Great Britain page first, to see whether someone has been stripping out the most valuable stamps.
Errors and Flaws
Despite the best efforts of post offices around the world, errors, flaws and tiny variants occasionally creep into the printing process, and these are sought after by collectors. It could be the wrong paper being used, or a mechanical malfunction which results in marginal printer's codes being printed directly onto the stamps. With modern lithographic methods, most flaws consist of tiny flecks or shadows which will only be spotted by those with the keenest of eyesight.