You have to update the screen like that:
pygame.display.flip()
to render what you just drew.
Your code should look like this:
import pygame
import time
pygame.init()
GREEN = (30, 156, 38)
WHITE = (255,255,255)
screen = pygame.display.set_mode((640, 480))
# draw on screen
screen.fill(WHITE)
pygame.draw.rect(screen, GREEN, (0,0,100,100))
# show that to the user
pygame.display.flip()
time.sleep(3)
Off-topic: You should also get the events to allow the user to close the window:
import pygame
from pygame.locals import QUIT
import time
pygame.init()
GREEN = (30, 156, 38)
WHITE = (255, 255, 255)
screen = pygame.display.set_mode((640, 480))
clock = pygame.time.Clock() # to slow down the code to a given FPS
# draw on screen
screen.fill(WHITE)
pygame.draw.rect(screen, GREEN, (0, 0, 100, 100))
# show that to the user
pygame.display.flip()
start_counter = time.time()
while time.time() - start_counter < 3: # wait for 3 seconds to elapse
for event in pygame.event.get(): # get the events
if event.type == QUIT: # if the user clicks "X"
exit() # quit pygame and exit the program
clock.tick(10) # limit to 10 FPS
# (no animation, you don't have to have a great framerate)
Note that you must put all of this into a game loop if you want to repeat it like a classic game.