$\newcommand{\PSP}{{\mathbb P}}$
Uniqueness can be proven this way: Let $C \subseteq \PSP^3_k$ be the twisted cubic curve. Furthermore let $P_1,P_2$ and $Q_1,Q_2$ be four points on $C$ with $P_1 \neq P_2$ and $Q_1 \neq Q_2$. Let $l_1$ be the line through $P_1, P_2$ and $l_2$ be the line through $Q_1,Q_2$. Now let $R$ be a point on $l_1 \cap l_2$, apart from $C$.
Then $l_1, l_2 \subseteq H$ for a certain plane $H \subseteq \PSP^3_k$. This plane intersects $C$ in at most three different points. So one must have $P_i = Q_j$ for certain $i,j$. As $R$ is a second common point of $l_1,l_2$ they must coincide, $l_1 = l_2$.
The proof of $\mathrm{Sec} C = \PSP^3_k$ can probably be done via the following gröbner base calculation (to be honest, the problem is, what is actually computed is only the defining ideal of the closure of $\mathrm{Sec} C$). Note that:
1) I used your parametrization of the secant variety in the variable vmat.
2) ideal() stands for ideal(0), it is the definining ideal of the closure of the image of the parametrization of $\mathrm{Sec} C$.
i1 : R=QQ[x_0..x_3]
o1 = R
o1 : PolynomialRing
i2 : S=QQ[s_0,s_1,t_0,t_1,u,v]
o2 = S
o2 : PolynomialRing
i3 : vmat={u*s_0^3+v*t_0^3,u*s_0^2*s_1+v*t_0^2*t_1,u*s_0*s_1^2+v*t_0*t_1^2,u*s_1^3+v*t_1^3}
3 3 2 2 2 2 3 3
o3 = {s u + t v, s s u + t t v, s s u + t t v, s u + t v}
0 0 0 1 0 1 0 1 0 1 1 1
o3 : List
i4 : phi=map(S,R,vmat)
3 3 2 2 2 2 3 3
o4 = map(S,R,{s u + t v, s s u + t t v, s s u + t t v, s u + t v})
0 0 0 1 0 1 0 1 0 1 1 1
o4 : RingMap S <--- R
i5 : ker phi
o5 = ideal ()
Note added: How to avoid using Bezout's theorem at the moment I have no simple idea, but I think for $\mathrm{Sec} C =\PSP^3_k$ a better proof is possible, which sheds light on the question if really every point of $\PSP^3_k-C$ lies on a secant of $C$:
If one takes an arbitrary point $P \notin C$ and projects from $P$, giving $\PSP^3_k - P \to \PSP^2_k$ and so $g:C \to \PSP^3_k - P \to \PSP^2$ then $g(C)$ should be a cubic curve in $\PSP^2_k$. As the genus of $g(C)$ is zero, the curve must be nodal or cuspidal. If it is nodal, the two points $R_1$ and $R_2$ of $C$ over the node $Q$ of $g(C)$ furnish a secant containing $P$. But in case $P$ lies on $\mathrm{Tan} C$, the tangent variety, then $g(C)$ is cuspidal with the cusp being the image of the tangent to $C$ through $P$. But then $g(C)$ can not be nodal too, because of the genus formula
$$p = \frac{1}{2}(3-1)(3-2) - n_c - n_n$$
where $n_c$ is the number of cusps and $n_n$ the number of nodes.
So in effect we see, that not every point of $\PSP^3_k-C$ lies on a secant of $C$, some lie only on a tangent - but the closure of the space of secants is indeed $\PSP^3_k$.