My 2000 Ford Ranger 6 Cyl 3.0 L has been overheating. Pretty sure its a radiator problem but odd symptoms?

Truck exhaust will puff moderate amount of white smoke (every now n again) on cold startup but will subside after engine warming up.Truck "Was" overheating until i put more coolant in but realised cap was steaming along with coolant reservoir (reservoir was also bubbling). So i bought a new radiator cap. I got a safety cap and after installing I drove a little and engine temp goes to red really fast. What could it be? Thermostat? Water pump? Blown head gasket?

I have the same truck (2001). I would do two things right away. One, if your fluid is not new, I would flush it, and two, I would remove the thermostat while flushing the fluid and keep it out after you are done to see if you have any problems. If you don't have any problems anymore, then put a new thermostat in (you should always put a new one in after changing the coolant).
Here is how to flush you coolant:

Sounds like a blown head gasket… White smoke from exhaust is one clue… Bubbling/overheating is another although that could be due to air pockets in the system or other issues… Stuck t-stat, clogged radiator, etc… Pull the oil dipstick and see if the end looks milky or foaming…= coolant in oil/internal head gasket leak into block area rather than combustion chamber area. Have a shop perform a pressure test of the cooling system or use a chemical kit which tests for the presence of hydrocarbons in the coolant due to blown head gasket… Pressure testers are sold or rented at parts stores if you want to test yourself… Chemical kits as well. They can also do a cylinder pressure test to see if one is low… Possible head gasket leak or other issue… Should not be lower than 15 percent of the highest values for any cylinder.

Start with a cooling system pressure or chemical/hydrocarbon test… Bleed any air from the cooling system if it was low on coolant… Check for external leaks… Install new t-stat and flush the system if it tests OK… Use a chemical flushing compound to help get out rust and scale… Sold at parts stores. Make sure cooling fans are operating properly, nothing is blocking the radiator and test/check coolant temp sensor.

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