Well, unfortunately Slovenian Railways don't sell tickets online yet, while Serbian do, but not for this type of route...c'est la vie
Although to be fair, it's not really essential to buy tickets in advance when traveling around Balkans, since in most cases fare doesn't depend on time of ticket purchase and almost none train require obligatory seat reservation. As result you can easily come to the station 10 min. before departure and buy needed ticket.
Regarding Venice-Belgrade route there are a few relatively cheap solutions to consider: a) catch local train from Venice to Gorizia (from 10,75 euro and 2-3 hours depending on connection, run often), Gorizia located right across from Slovenian Nova Gorica (actually historically it's one town), so you just need to walk from Italian to Slovenian side (also possible to take town bus) and catch bus to Ljubljana or train to Jesenice. Next catch direct overnight train to Belgrade departs from Ljubljana 21:16 (or 20:12 from Jesenice), arr. to Belgrade 6:16. Full fare ticket Ljubljana-Belgrade cost 49,2 euro; b) catch local train from Venice to Trieste (roughly 2 hours and 11,35 euro), then bus to Rijeka (few times per day) or even Zagreb (once a day), while then catch same overnight train to Belgrade (dep. Zagreb 23:55, full fare ticket is around 25 euro); c) if the journey isn't tomorrow, then also can be used a bit weird, but can be rather cheap option - RyanAir flight Venice(Treviso)-Budapest and then direct train Budapest-Belgrade (full fare is 15 euro)
I used to believe it is cheaper by train from Moscow to Belgrade, but after checking airfares it doesn't look that I could save much by train.
Though direct train (actually it's only one carriage) isn't very expensive, but still flights can be quite comparable here, unless you ready to travel with many changes and 'breaks' of tickets. While in your case (at least judging from your current IP), cheapest way to reach Belgrade might be actually to get bus to Tallinn/Riga, then fly to Stockholm (RyanAir), while from there directly to Belgrade by WizzAir or something like that, plus it can save quite a lot of time
Still interested about travel between Cz or Viena and Belgrade...
In both case everything is relatively easy, you just need to buy a bit in advance discounted tickets to Budapest (either Vienna-Budapest or Prague(if it's what you mean by 'Cz')-Budapest), here both Czech and Austrian Railways do sell it online, while already in Hungary get cheap 15 euro ticket Budapest-Belgrade