I've never heard of Net14 before and don't know how it differs from APRS in general, but the best band for APRS activity (including using PSK63) 24/7 seems to be 30m.
You need the software APRS Messenger which you can get from this Yahoo group: http://uk.groups.yahoo.com/group/cross_country_wireless/ where you'll also find help and advice on using it if necessary. This is all you need to send and receive APRS text messages but it can be fun to use an APRS client such as APRSISCE (obtainable froim this Yahoo group: http://groups.yahoo.com/group/aprsisce) so you can see on a map the position of stations whose packets you receive. APRS over PSK63 on 30m is operated using USB with a dial frequency of 10.137600 MHz and an audio frequency of 2100Hz (the latter is an option selected within the APRS Messenger software.) You cannot use a regular PSK63 program to participate in this because the APRS over PSK63 protocol uses checksumming to ensure the validity of packets. There are probably a lot of other questions which have already been answered (or can be asked) in the aforementioned Yahoo groups. This is a very interesting use of PSK63 which appears to provide a more robust method of sending APRS over HF than using 300baud packet. Julian, G4ILO