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In most cases, sensitive teeth is caused by exposed dentin, the layer next to the enamel. A lot of things can cause dentin to be exposed. One most common is improper toothbrushing method. Too much pressure applied during toothbrushing using a hard bristled toothbrush causes abrasion on the enamel layer, exposing the dentin layer beneath it. Most common example of this is cervical abrasions, found in the "neck" portion of the tooth crown.
The tooth can also be bruised or abraded fom dntal instrumentations, especially after a restorative procedure. Accidental biting on hard substances can also bruised the tooth.
Another cause of tooth sensitivity is exposure of the root portion of the tooth due to gingival recession.

There are specialized toothpaste that claims to have a desensitizing action. There action is to seal tubules found in dentin. Use this toothpaste on your regular toothbrushing schedules.
Use a soft bristled toothbeush so as not to aggravate your teeth's condition. While using soft bristled toothbrush, you stil need to lighten your brushing strokes.
Smoking can cause gum recession, and if gums recede, root surfaces are exposed which are usually sensitive parts of the tooth. You may not just suffer from tooth sensitivity from smoking' you can also have gum problems which may eventually progress inot periodontitis.
Acidic food are not friendly to your enamel, especially when it is bruised. They eat up enamel structure and eventually exposed the sensitive dentin beneath it.