One limitation on market value is that transactions on the open market involve small minority interests in publicly traded companies. Typically, when an acquiring company makes a takeover bid, it will offer a premium to the recent market price. That premium reflects the added value of having a controlling interest versus being a minority shareholder.
Looking at the market value of a firm's equity lets you compare the relative sizes of different companies more easily. It's not the only way to put a value on a company, but it gives a useful starting point for your research.