Hey Lin!
Actually, your lionfish is venomous, not poisonous so everyone in your tank - including yourself - should be ok unless you come in contact with its fins. I'm also willing to bet that your other fish are aware of this also so they should be ok. However, depending on what type of lionfish you have (I'm assuming a dwarf lionfish, right?), you might have to be careful because even the smaller versions can swallow some pretty big stuff.
You might want to try feeding him krill. Since lionfish are reclusive, odds are that yours isn't going to be very happy about coming into the open if you just dump some food in and even if yours wasn't afraid of a net, you probably don't want to take the risk of him getting caught in the net either...obviously it could be very painful for both parties if its fins got caught in the net.
When I had a lionfish, I fed frozen krill that I would thaw out in a cup of water from the tank like you mentioned. If your fish won't come to the food, my suggestion would be to use wooden or clear plastic skewers so you can bring the food to it without having to put yourself in jeopardy. This might take a little experimenting though because you probably don't want to keep pushing food in its face but you should be able to tell when it is getting disgruntled when it starts pointing its dorsal fins at you or the food.
You may also want to try soaking some food in garlic as well. I know it might not work for everyone or in every situation but IME, garlic seems to make food a lot more interesting to picky eaters.
The last resort would be live foods but the problem is that lionfish don't really come across all that many guppies, or other freshwater fish for that matter, too often it's very possible for your fish to eat copious amounts of guppies and still die of malnutrition. I think the better alternative would be to "gut pack" any live foods by feeding them marine flake foods or better yet, gut packing some ghost shrimp. Again, that would be the last resort and even then, you'd still want to keep trying to get him to eat something better.
I know it might sound bad but the only other 'trick' I can think of right now would be to refuse offering live foods and hope that it will eventually get hungry enough to eat anything. The thing to keep in mind here is that you might find out that your lionfish will prefer eating large but less frequent meals. This means that A) you probably won't have to feed it every day, B) it probably isn't going to starve to death if it doesn't eat for a week and, C) trying to 'starve' it into submission could be a test of your patience.
Hopefully someone else will have some better advice for you. It might help to know what type of lionfish you have exactly as well. Personally, I think lionfish are just about the coolest thing I have ever kept but I can understand your concerns. For whatever reason, it sounds like lionfish can be a hit or miss type of thing where one wouldn't think twice about eating a shoe if you gave him one while his brother won't eat anything unless it has a pulse. It is very possible to change that though.