1. Find an item you can afford and looks promising in the list
2. Click on the item to open the item page
3. (optional)Check the price history of the item to see if the price is stable or dropping
4. If the price is stable, buy some from the npc (you can find detailed information about the item on the linked wiki pages)
5. List the item on either ah or bazaar
6. After it sold, repeat

Volume is how many items are sold per day on average. The higher the volume the easier it is to sell your item.

For bazaar items this is how many items are sold on bazaar per day, for auction house items this is how many items are sold on auction house per day.

The median is what an item usually sells for, you can learn more with this video.

This is a good indicator of the actual price of an item as it is not influenced by outliers like the average price is.

The displayed purchase cost is the sum of coins + item purchase cost required to get an item from the NPC.
For example Wither Goggles purchase cost is 5m Skyblock Coins combined with the cost of Shadow Goggles both of which you hand to the Ophelia NPC

Yes, many NPC items have a limit to how many items you can buy from them per day.
This is usually 640 items per day for bazaar items.

Some npc are only accessible during special skyblock events. If that event is not active you can't currently do the flip.
Note that you can learn from the price difference.
Buy more when the event is active and sell them later when its not. Doing it this way with a bit of waiting can net you way more profit with npc flips.