TheWingMan,
if you want to get big arms u gotta understand a few things :
1- the size of the arms is in proportion with the size of the whole body, meaning that the more weight you gain, the bigger your arms will get. since you have very skinny arms, I am sure you are a skinny guy.
so if you want bigger arms, you need to gain weight by eating more and training your whole body especially legs, back, chest and shoulders. the back help train the biceps, shoulders and chest help train the triceps.
2- the main muscles in the arms are : shoulders, triceps, biceps and forearms.
the biceps have two head whereas the triceps have 3. if you want bigger arms consider training the triceps in more angles because they have more head which mean that they are bigger than the biceps. you only have the illusion that the biceps are bigger but that's not true.
3- u can train arms 1-2 times per week. train why heavy weights and dude sets till failure.
4-eat eat eat! and rest because your arms need to heal.
5- if you are like me, you probably have weak forearms so train them well because you are only as strong as your weakest muscle.
6-never skip any body part especially legs, because legs are the biggest muscles in the body , which means they will help you very much in gaining mass which well help you develop bigger arms indirectly, not to forget that training legs increase testosterone in the body.