It's not clear to me exactly where the high-score that you're interested in is stored, but the code below should be what you need to check if the file exists and append to it if desired. I prefer this method to the "try/except".
import os
player = 'bob'
filename = player+'.txt'
if os.path.exists(filename):
append_write = 'a' # append if already exists
else:
append_write = 'w' # make a new file if not
highscore = open(filename,append_write)
highscore.write("Username: " + player + '\n')
highscore.close()