Neutral air is your friend. Use it often. It's a good KO move, it out prioritizes a lot of attacks and it can interrupt your opponent when they're trying to combo you.
Luigi is king when it comes to punishing laggy attacks. His up special will kill most characters around 50%. It's best to use near the ledge so if you miss you can fast fall and grab the ledge.
Luigi's ground game is okay. His jabs are fast and have a lot of priority. His forward smash is very powerful. Even more so if you angle it up. Fireballs can annoy opponents and create openings. Up smash is powerful and has deceptive range if your opponent is not too far behind you.
Multiple up tilts are very good at racking up damage at low percentage. Especially for fast fallers. It also creates set ups in the air. After they're out of up tilt range, use a netural air to send them higher. Now do your best to keep them in the air as long as possible while you juggle them with all sorts of air attacks.
Down throw is good for going into uptilts
Back throw is a decent killer at high percentage.
If your opponents gets knocked down and you're close by, immediately start fire balling them. You might fireball lock them. They will be unable to move or get up while you pelt them with fireballs until they're out of range.
Luigi's running attack isn't very good. Don't use it often.
Don't use cyclone unless you're kind of close, otherwise, it might end right in front of your opponent and cyclone has ending lag. Don't be too predictable with it either because like I said, it has ending lag. You can be punished for using it.
It's best not to use green missile as an attack because it's weak unless charged and has ending lag if you land on the ground with it. Green missile is best used as a recovery.
Cyclone can give Luigi a lot of height if you use it immediately after jumping then rapidly push b. When you get knocked away and you don't think you have enough height to green missile or jump back, use it. Be absolutely sure you use it immediately ater jumping. If you wait too long then you won't gain any height and will screw yourself over.
Some fire jump punch sets ups are:
Jab, jab, up b
Jab, jab, down tilt (33% chance they will trip) If they trip, up b them. When your opponent has 100% or more damage, down tilt can no longer trip them.
up b out of the shield if they make the mistake of getting ontop of you
Side step attack, up b (works really well on down airs that send them straight down)