This is highly dependant on the game - some games support 2 player consecutively (like Pac-Man or Super Mario Bros), others support 2 players simultaneously (like the Street Fighter games). It's not something that can be configured in the emulator.
If you have just one gamepad (joystick + buttons) but the game expects 2 players, then you can't change it - the 2nd pair of controls would insert the coin (Select) and also use Start to enter the game.
What game are you trying to play ?