First make sure the belt is tight enough, it can stretch over time, and even after first use.
Inspect the belt for any damage or shiny spots. Look for any moisture or oils, belt should be dry and clean.
If you still get the squeal and want to pinpoint it, pick one of these up at your local harbor freight or amazon...
Mechanics Stethoscope $5 they are dirt cheap and come in handy for finding the sources of other engine noises. Heck, while you are at it, here my 2 other favorite cheap but very handy tools, may help you find any leak or wear that is hard to see from above the car.
Mirror, and
Magnet. That magnet on a stick has saved me so much frustration when working on engines, dropping a nut/bolt, Wrench, socket etc down into the engine compartment where you can not reach, this thing gets it right out, also easier to recover things that fall onto the ground under the car without having to get on my hands and knees or on my back under the car.
You said it happens on start-up and acceleration, have someone in the driver seat starting or hitting the gas to cause the squeal to occur and chase down the source of the noise with the stethoscope. Then go from there. But the most common cause is a belt that just needs a little more tension.
Also, make sure all your fluids are at the proper level and in good condition.