Repellents that contain such chemicals such as DEET do repel foraging imported fire ants. However, spraying these repellents will not deter "angry" ants from emerging out of disturbed mounds before they start biting and stinging.
The best advice for working in fire ant infested areas is to look for mounds so you can avoid stepping on them. Also wear protective clothing, such as boots with pant legs tucked inside, to help you see the fire ants before they can sting. Dust baby or talcum powder on hard objects such as shovel or rake handles to prevent fire ants from crawling up these surfaces. As long as the talcum powder is kept dry, it will prevent fire ants from climbing up the hard objects to sting. Talcum powder can also be dusted on rubber boots to prevent fire ants from climbing onto your body.