One of the most interesting questions I've seen so far on Bayt! I would have wished however that you be more specific about the definition of a word, if we're talking on a linguistic level: a word is made up of a root, and prefixes or suffixes. However if we're talking about semantics & etymology and how come certain words developed certain meanings, well this is a longer story... First of all we have to say that there is no logical connection between the letters that make up the word " Chair " and the actual chair itself, and scientists believe that such words came about with the development of the language itself which means a VERY long time ago! How did that happen remains unfamiliar till this day...it just did .....
As for the other part of the question, concerning the actual process of learning vocabulary, well for children as they are learning how to talk at the age of1-2, they process the meaning of the sound they're hearing from their parents with the actions being done at the same time or the object being used, and simply record them in their brains and later on start using them. As for grown-ups or people learning foreign languages at a later age, that's a different process depending on the nature of the education they're receiving, in general we can say that when learning new vocab adults make a comparison, this comparison could be done with the simple act of giving the equivalent of the word in the mother language, or with signs that travelers use when completely unable to communicate with natives.....
Again a really excellent question !