How many chips does each player start with?
Enough to cover 50 to 100 big blinds. For a $20 buy-in at 0.10/0.25 blinds that is 80 big blinds, which works out to roughly 20 of the smallest chip, 12 of the next, and 4 of the third. Start from the buy-in and the blinds, never from the chip set.
The instinct is to open the case, see five colours, and divide them up. Do it the other way round. Decide the buy-in, decide what that should be in big blinds, and only then check whether your set can express that amount.
Three denominations is usually right and four is the practical maximum. Every extra colour is another value somebody has to be reminded of twice a night, and another chance of a hand stopping while change gets made.
The smallest chip matters more than the biggest. A player needs to be able to post the small blind all evening without breaking a larger chip, so give everyone about twenty of the smallest denomination regardless of the buy-in.
The full answer
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