Just to clarify what others have said on this subject.
If you have only a single PSTN line, then it can only carry a single call at any given time. This is not a restriction in 3CX but in the way that telephone systems in gereral work. While your telephone provider may support services such as call waiting (you hear a tone to inform you that someone else is trying to call you), call hold etc., as far as 3CX is concerned, there is still only one call in progress. If call waiting is not enabled on your line, then any other callers will simply get engaged tone.
The possible solutions to your problem are
1. Install one or more pstn lines (connected to your voip gateway) depending on the number of simultaneous lines that you wish to be able to handle. Your telephone provider should be able to set-up hunting on these so that all callers can dial the same number with the exchange presenting the calls to you on the next available line.
2. Check with your telephone provider to see if you pstn line supports call forwarding on busy. If so, then you could try to forward calls to your voip number when your pstn line is busy.
As indicated by other posters, once you can receive additional calls, then the next issue is to configure 3CX to handle the calls in the manner that you want.
Hope this helps to clarify the options.
Des