Simpson briefly gave Latics the lead with a superb opening goal before Paul Dickov's League One outfit went down 5-1 at Anfield in the third round last season.
The 27-year-old former Cambridge, Coventry and Huddersfield forward was Oldham's cup hero once more at the weekend as his brace inspired a 3-2 upset triumph over Nottingham Forest and set up a reunion with the Reds later this month.
Brendan Rodgers' men saw off the spirited challenge of Blue Square Bet Premier outfit Mansfield 2-1 in the wake of Sunday afternoon's draw, with the help of a disputed Luis Suarez strike.
"It will be a brilliant occasion and let's hope it will be televised after we caused an upset in the last round," Simpson told Latics' official website.
"I was settling down to watch the Mansfield v Liverpool tie when the draw was made and I couldn't believe it. It is a special draw and let's hope we can avenge last year's defeat.
"As soon as the draw was made the lads began contacting each other and everyone was excited. They thought it would be just our luck that Liverpool lost, but they scraped through.
"Non-league Mansfield gave a good account of themselves and, but for a Liverpool goal which should not have stood, they would have earned a replay.
"It will be similar (to the Forest game) in that nobody will expect us to win. Let's hope we enjoy the day and we can experience more cup magic and cause another upset," he said.