Think of building a PC like doing a jigsaw, if a part doesn't fit then it either doesn't go there or you have it the wrong way around.
Start with your case, open it up and screw the hard drive / optical drives in. The back of both should face the inside of the case for easy cable access.
Next you want attach the motherboard, be sure to put the backing plate on as you slot it in to the case. You may also have some (dont know the technical name) screws that need to be screwed in to the case that raise the motherboard slightly so the back plate is aligned with the back of the case. This will vary from case to case.
When attatching the processor to the motherboard it will only go one way, remember to put the thermal paste on it between the CPU and heatsink. Likewise for the ram that will only go one way, and you cant really get any PCI expansion cards the wrong way around.
Its just a case of wiring the power, sata, usb, and wires for the power / reset buttons on the case up then. Again all motherboards as different to refer to the manual if you are unsure where to connect the CPU and any case fans to, again you should find its pretty hard to connect the wrong wire to the wrong place.
That's summing it very basically, however if you take your time and dont rush i think it would be pretty hard to mess something up. I'm sure you can find some YouTube videos that will guide you through building a basic pc, have a look at your current pc and try taking the parts out and putting it back together so you have a good idea what your doing.
As Trebor and Dark Scyth say any problems post here and we can try help, it sounds a lot harder than it actually is to build a PC.