In order to develop shapely arms you will definitely want to perform some triceps exercise. This muscle is one that predominately forms the upper portion of your arm and when developed is extremely aesthetically pleasing.
There are generally two types of triceps exercise variations that you can perform: one handed movements and two handed movements. The one handed ones are very isolated and are good for really bring up this body part if it is lacking. Some people who participate in certain sports will see one side being weaker than the other so this is a good way to overcome this problem.
When performing triceps exercise you always want to ensure that your elbow tries to stay directly in line with the shoulder joint. This will help keep the muscle moving on the right track and prevent any pain from developing. Since this is quite a long limb the force of gravity acting on the hand (due to the lever system) will put a lot of pressure on the shoulder joints and tendons so it's critical you are aware of this.
Furthermore, when performing any movements where the weight is being placed above the head, watch out for the form your back takes. Far too often we start swaying our back when weight moves above and this again creates unnecessary pressure.
Good movements to perform for this muscle group are kickbacks, overhead extensions, cable pull-downs, triangle push-ups, bench presses, closed grip bench presses, barbell extensions and dips. Most of these can easily be performed in the comfort of your own home with a pair of store-bought dumbbells or with some rubber tubing.