Storing hashed passwords I'm a beginner and am self taught and was hoping I could get help from others more educated than me to show me what bad practices I might be forming before I go on further.

P.S. This program is just for me to learn, I'm not actually storing passwords with it.

#!/usr/bin/env python
# -*- coding: utf-8 -*-
import sys

def openPassFile():
    try:
        passwordFile = open('hashwork.txt', 'a')
        return passwordFile
    except IOError as e:
        print("I/O Error({0}): {1}".format(e.errno, e.strerror))
        quit

def closePassFile(passwordFile):
    try:
        passwordFile.close()
    except IOError as e:
        print("I/O Error({0}): {1}".format(e.errno, e.strerror))
        quit

def randomValue(length):
    import random
    salt_chars = 'abcdefghijklmnopqrstuvwxyz0123456789'
    return ''.join(random.choice(salt_chars) for x in range(length))

def askforUsername():
    while True:
        print("Please enter the username you would like to use:")
        username = raw_input()
        return username

def askforPassword():
    import getpass, hashlib
    while True:
        print("What password would you like to create?")
        salt = randomValue(16)
        hashedPassword1 = hashlib.sha256(salt+getpass.getpass()).hexdigest()
        print("\nPlease enter password again.")
        hashedPassword2 = hashlib.sha256(salt+getpass.getpass()).hexdigest()
        if hashedPassword1 == hashedPassword2:
            return hashedPassword2, salt
            break
        else:
            print("Your passwords do not match. Please retry")

def storeInfo(username, hashedPass, salt):
    passwordFile = openPassFile()
    passwordFile.write(username + " | " + hashedPass + " | " + salt + "\n")
    closePassFile(passwordFile)

username = askforUsername()         
hashedPass, salt = askforPassword()
storeInfo(username, hashedPass, salt)
sys.exit()
SHA256 is not a secure password hash because it is fast. See How to securely hash passwords? on security.se for details.
It's not obvious that random is good enough to generate salts. While the requirments for salts are lower than those for keys, you still need a decent RNG. I recommend using SystemRandom.